Polymer compositions and methods

ABSTRACT

The present invention encompasses polyurethane compositions comprising aliphatic polycarbonate chains. In one aspect, the present invention encompasses polyurethane foams, thermoplastics and elastomers derived from aliphatic polycarbonate polyols and polyisocyanates wherein the polyol chains contain a primary repeating unit having a structure: 
     
       
         
         
             
             
         
       
     
     In another aspect, the invention provides articles comprising the inventive foam and elastomer compositions as well as methods of making such compositions.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 15/833,155, filed Dec. 6, 2017 (now U.S. Pat. No. 10,351,654),which is a continuation of U.S. patent application Ser. No. 15/206,402,filed Jul. 11, 2016 (now U.S. Pat. No. 9,884,937), which is acontinuation of U.S. patent application Ser. No. 14/234,482, filed Jan.23, 2014 (now U.S. Pat. No. 9,453,100), which claims priority to U.S.provisional patent application No. 61/511,543, filed Jul. 25, 2011, theentire contents of each of which are hereby incorporated by reference.

GOVERNMENT SUPPORT

This invention was made with government support under grant numberDE-FE0002474 awarded by the Department of Energy. The government hascertain rights in the invention.

FIELD OF THE INVENTION

This invention pertains to the field of polymers. More particularly, theinvention pertains to polyurethane foams and thermoplasticsincorporating aliphatic polycarbonate polyols having a high percentageof —OH end groups.

SUMMARY OF THE INVENTION

In one aspect, the present invention encompasses polyurethane foams,thermoplastics and elastomers derived from aliphatic polycarbonatepolyols and polyisocyanates wherein the polyol chains contain a primaryrepeating unit having a structure:

-   -   where R¹, R², R³, and R⁴ are, at each occurrence in the polymer        chain, independently selected from the group consisting of —H,        fluorine, an optionally substituted C₁₋₄₀ aliphatic group, an        optionally substituted C₁₋₂₀ heteroaliphatic group, and an        optionally substituted aryl group, where any two or more of R¹,        R², R³, and R⁴ may optionally be taken together with intervening        atoms to form one or more optionally substituted rings        optionally containing one or more heteroatoms.

In certain embodiments, such aliphatic polycarbonate chains are derivedfrom the copolymerization of carbon dioxide with one or more epoxidesubstrates. Such copolymerizations are described and exemplified inpublished PCT application WO/2010/028362 the entirety of which isincorporated herein by reference. In some embodiments, the aliphaticpolycarbonate chains are derived from ethylene oxide, propylene oxide,or optionally substituted C₃₋₃₀ aliphatic epoxides, or mixtures of twoor more of these. In some embodiments, the aliphatic polycarbonatechains have a number average molecular weight (M_(N)) less than about20,000 g/mol. In certain embodiments, the aliphatic polycarbonatepolyols have a functional number of between about 1.8 and about 6.

In another aspect, the present invention encompasses urethanecompositions comprising aliphatic polycarbonates derived from thealternating copolymerization of one or more epoxides and carbon dioxide.In certain embodiments, the inventive urethane compositions comprisefoams. In certain embodiments, the inventive urethanes comprisethermoplastic polyurethanes. In certain embodiments, the inventiveurethanes comprise polyurethane molding compositions. In certainembodiments, the inventive urethanes comprise polyurethane sheet, bar,rod, or tube stock.

In another aspect, the present invention encompasses methods of makingsuch foams and thermoplastic compositions. In certain embodiments, themethods comprise a step of contacting the aliphatic polycarbonate polyolwith one or more isocyanate compounds under conditions to promote thechain extension of cross-linking of the polyol chains by formation ofurethane linkages.

Definitions

Definitions of specific functional groups and chemical terms aredescribed in more detail below. For purposes of this invention, thechemical elements are identified in accordance with the Periodic Tableof the Elements, CAS version, Handbook of Chemistry and Physics, 75^(th)Ed., inside cover, and specific functional groups are generally definedas described therein. Additionally, general principles of organicchemistry, as well as specific functional moieties and reactivity, aredescribed in Organic Chemistry, Thomas Sorrell, University ScienceBooks, Sausalito, 1999; Smith and March March's Advanced OrganicChemistry, 5^(th) Edition, John Wiley & Sons, Inc., New York, 2001;Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., NewYork, 1989; Carruthers, Some Modern Methods of Organic Synthesis, 3^(rd)Edition, Cambridge University Press, Cambridge, 1987; the entirecontents of each of which are incorporated herein by reference.

Certain compounds of the present invention can comprise one or moreasymmetric centers, and thus can exist in various stereoisomeric forms,e.g., enantiomers and/or diastereomers. Thus, inventive compounds andcompositions thereof may be in the form of an individual enantiomer,diastereomer or geometric isomer, or may be in the form of a mixture ofstereoisomers. In certain embodiments, the compounds of the inventionare enantiopure compounds. In certain embodiments, mixtures ofenantiomers or diastereomers are provided.

Furthermore, certain compounds, as described herein may have one or moredouble bonds that can exist as either the Z or E isomer, unlessotherwise indicated. The invention additionally encompasses thecompounds as individual isomers substantially free of other isomers andalternatively, as mixtures of various isomers, e.g., racemic mixtures ofenantiomers. In addition to the above-mentioned compounds per se, thisinvention also encompasses compositions comprising one or morecompounds.

As used herein, the term “isomers” includes any and all geometricisomers and stereoisomers. For example, “isomers” include cis- andtrans-isomers, E- and Z-isomers, R- and S-enantiomers, diastereomers,(D)-isomers, (L)-isomers, racemic mixtures thereof, and other mixturesthereof, as falling within the scope of the invention. For instance, astereoisomer may, in some embodiments, be provided substantially free ofone or more corresponding stereoisomers, and may also be referred to as“stereochemically enriched.”

Where a particular enantiomer is preferred, it may, in some embodimentsbe provided substantially free of the opposite enantiomer, and may alsobe referred to as “optically enriched.” “Optically enriched,” as usedherein, means that the compound or polymer is made up of a significantlygreater proportion of one enantiomer. In certain embodiments thecompound is made up of at least about 90% by weight of a preferredenantiomer. In other embodiments the compound is made up of at leastabout 95%, 98%, or 99% by weight of a preferred enantiomer. Preferredenantiomers may be isolated from racemic mixtures by any method known tothose skilled in the art, including chiral high pressure liquidchromatography (HPLC) and the formation and crystallization of chiralsalts or prepared by asymmetric syntheses. See, for example, Jacques, etal., Enantiomers, Racemates and Resolutions (Wiley Interscience, NewYork, 1981); Wilen, S. H., et al., Tetrahedron 33:2725 (1977); Eliel, E.L. Stereochemistry of Carbon Compounds (McGraw-Hill, N Y, 1962); Wilen,S. H. Tables of Resolving Agents and Optical Resolutions p. 268 (E. L.Eliel, Ed., Univ. of Notre Dame Press, Notre Dame, Ind. 1972).

The term “epoxide”, as used herein, refers to a substituted orunsubstituted oxirane. Such substituted oxiranes include monosubstitutedoxiranes, disubstituted oxiranes, trisubstituted oxiranes, andtetrasubstituted oxiranes. Such epoxides may be further optionallysubstituted as defined herein. In certain embodiments, epoxides comprisea single oxirane moiety. In certain embodiments, epoxides comprise twoor more oxirane moieties.

The term “polymer”, as used herein, refers to a molecule of highrelative molecular mass, the structure of which comprises the multiplerepetition of units derived, actually or conceptually, from molecules oflow relative molecular mass. In certain embodiments, a polymer iscomprised of substantially alternating units derived from CO₂ and anepoxide (e.g., poly(ethylene carbonate). In certain embodiments, apolymer of the present invention is a copolymer, terpolymer,heteropolymer, block copolymer, or tapered heteropolymer incorporatingtwo or more different epoxide monomers. With respect to the structuraldepiction of such higher polymers, the convention of showing enchainmentof different monomer units separated by a slash may be used herein

These structures are to be interpreted to encompass copolymersincorporating any ratio of the different monomer units depicted unlessotherwise specified. This depiction is also meant to represent random,tapered, block co-polymers, and combinations of any two or more of theseand all of these are implied unless otherwise specified.

The terms “halo” and “halogen” as used herein refer to an atom selectedfrom fluorine (fluoro, —F), chlorine (chloro, —Cl), bromine (bromo,—Br), and iodine (iodo, —I).

The term “aliphatic” or “aliphatic group”, as used herein, denotes ahydrocarbon moiety that may be straight-chain (i.e., unbranched),branched, or cyclic (including fused, bridging, and spiro-fusedpolycyclic) and may be completely saturated or may contain one or moreunits of unsaturation, but which is not aromatic. Unless otherwisespecified, aliphatic groups contain 1-40 carbon atoms. In certainembodiments, aliphatic groups contain 1-20 carbon atoms. In certainembodiments, aliphatic groups contain 3-20 carbon atoms. In certainembodiments, aliphatic groups contain 1-12 carbon atoms. In certainembodiments, aliphatic groups contain 1-8 carbon atoms. In certainembodiments, aliphatic groups contain 1-6 carbon atoms. In someembodiments, aliphatic groups contain 1-5 carbon atoms, in someembodiments, aliphatic groups contain 1-4 carbon atoms, in someembodiments aliphatic groups contain 1-3 carbon atoms, and in someembodiments aliphatic groups contain 1 or 2 carbon atoms. Suitablealiphatic groups include, but are not limited to, linear or branched,alkyl, alkenyl, and alkynyl groups, and hybrids thereof such as(cycloalkyl)alkyl, (cycloalkenyl)alkyl or (cycloalkyl)alkenyl.

The term “heteroaliphatic,” as used herein, refers to aliphatic groupswherein one or more carbon atoms are independently replaced by one ormore atoms selected from the group consisting of oxygen, sulfur,nitrogen, or phosphorus. In certain embodiments, one to six carbon atomsare independently replaced by one or more of oxygen, sulfur, nitrogen,or phosphorus. Heteroaliphatic groups may be substituted orunsubstituted, branched or unbranched, cyclic or acyclic, and includesaturated, unsaturated or partially unsaturated groups.

As used herein, the term “bivalent C₁₋₈ (or C₁₋₃) saturated orunsaturated, straight or branched, hydrocarbon chain”, refers tobivalent alkyl, alkenyl, and alkynyl, chains that are straight orbranched as defined herein.

The term “unsaturated”, as used herein, means that a moiety has one ormore double or triple bonds.

The terms “cycloaliphatic”, “carbocycle”, or “carbocyclic”, used aloneor as part of a larger moiety, refer to a saturated or partiallyunsaturated cyclic aliphatic monocyclic or polycyclic ring systems, asdescribed herein, having from 3 to 12 members, wherein the aliphaticring system is optionally substituted as defined above and describedherein. Cycloaliphatic groups include, without limitation, cyclopropyl,cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl,cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, norbornyl,adamantyl, and cyclooctadienyl. In some embodiments, the cycloalkyl has3-6 carbons. The terms “cycloaliphatic”, “carbocycle” or “carbocyclic”also include aliphatic rings that are fused to one or more aromatic ornonaromatic rings, such as decahydronaphthyl or tetrahydronaphthyl,where the radical or point of attachment is on the aliphatic ring. Incertain embodiments, the term “3- to 7-membered carbocycle” refers to a3- to 7-membered saturated or partially unsaturated monocycliccarbocyclic ring. In certain embodiments, the term “3- to 8-memberedcarbocycle” refers to a 3- to 8-membered saturated or partiallyunsaturated monocyclic carbocyclic ring. In certain embodiments, theterms “3- to 14-membered carbocycle” and “C₃₋₁₄ carbocycle” refer to a3- to 8-membered saturated or partially unsaturated monocycliccarbocyclic ring, or a 7- to 14-membered saturated or partiallyunsaturated polycyclic carbocyclic ring.

The term “alkyl,” as used herein, refers to saturated, straight- orbranched-chain hydrocarbon radicals derived from an aliphatic moietycontaining between one and six carbon atoms by removal of a singlehydrogen atom. Unless otherwise specified, alkyl groups contain 1-12carbon atoms. In certain embodiments, alkyl groups contain 1-8 carbonatoms. In certain embodiments, alkyl groups contain 1-6 carbon atoms. Insome embodiments, alkyl groups contain 1-5 carbon atoms, in someembodiments, alkyl groups contain 1-4 carbon atoms, in some embodimentsalkyl groups contain 1-3 carbon atoms, and in some embodiments alkylgroups contain 1-2 carbon atoms. Examples of alkyl radicals include, butare not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl,iso-butyl, sec-butyl, sec-pentyl, iso-pentyl, tert-butyl, n-pentyl,neopentyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, n-decyl, n-undecyl,dodecyl, and the like.

The term “alkenyl,” as used herein, denotes a monovalent group derivedfrom a straight- or branched-chain aliphatic moiety having at least onecarbon-carbon double bond by the removal of a single hydrogen atom.Unless otherwise specified, alkenyl groups contain 2-12 carbon atoms. Incertain embodiments, alkenyl groups contain 2-8 carbon atoms. In certainembodiments, alkenyl groups contain 2-6 carbon atoms. In someembodiments, alkenyl groups contain 2-5 carbon atoms, in someembodiments, alkenyl groups contain 2-4 carbon atoms, in someembodiments alkenyl groups contain 2-3 carbon atoms, and in someembodiments alkenyl groups contain 2 carbon atoms. Alkenyl groupsinclude, for example, ethenyl, propenyl, butenyl, 1-methyl-2-buten-1-yl,and the like.

The term “alkynyl,” as used herein, refers to a monovalent group derivedfrom a straight- or branched-chain aliphatic moiety having at least onecarbon-carbon triple bond by the removal of a single hydrogen atom.Unless otherwise specified, alkynyl groups contain 2-12 carbon atoms. Incertain embodiments, alkynyl groups contain 2-8 carbon atoms. In certainembodiments, alkynyl groups contain 2-6 carbon atoms. In someembodiments, alkynyl groups contain 2-5 carbon atoms, in someembodiments, alkynyl groups contain 2-4 carbon atoms, in someembodiments alkynyl groups contain 2-3 carbon atoms, and in someembodiments alkynyl groups contain 2 carbon atoms. Representativealkynyl groups include, but are not limited to, ethynyl, 2-propynyl(propargyl), 1-propynyl, and the like.

The term “alkoxy”, as used herein refers to an alkyl group, aspreviously defined, attached to the parent molecule through an oxygenatom. Examples of alkoxy, include but are not limited to, methoxy,ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy, neopentoxy, andn-hexoxy.

The term “acyl”, as used herein, refers to a carbonyl-containingfunctionality, e.g., —C(═O)R′, wherein R′ is hydrogen or an optionallysubstituted aliphatic, heteroaliphatic, heterocyclic, aryl, heteroarylgroup, or is a substituted (e.g., with hydrogen or aliphatic,heteroaliphatic, aryl, or heteroaryl moieties) oxygen or nitrogencontaining functionality (e.g., forming a carboxylic acid, ester, oramide functionality). The term “acyloxy”, as used here, refers to anacyl group attached to the parent molecule through an oxygen atom.

The term “aryl” used alone or as part of a larger moiety as in“aralkyl”, “aralkoxy”, or “aryloxyalkyl”, refers to monocyclic andpolycyclic ring systems having a total of five to 20 ring members,wherein at least one ring in the system is aromatic and wherein eachring in the system contains three to twelve ring members. The term“aryl” may be used interchangeably with the term “aryl ring”. In certainembodiments of the present invention, “aryl” refers to an aromatic ringsystem which includes, but is not limited to, phenyl, biphenyl,naphthyl, anthracyl and the like, which may bear one or moresubstituents. Also included within the scope of the term “aryl”, as itis used herein, is a group in which an aromatic ring is fused to one ormore additional rings, such as benzofuranyl, indanyl, phthalimidyl,naphthimidyl, phenantriidinyl, or tetrahydronaphthyl, and the like. Incertain embodiments, the terms “6- to 10-membered aryl” and “C₆₋₁₀ aryl”refer to a phenyl or an 8- to 10-membered polycyclic aryl ring.

The terms “heteroaryl” and “heteroar-”, used alone or as part of alarger moiety, e.g., “heteroaralkyl”, or “heteroaralkoxy”, refer togroups having 5 to 14 ring atoms, preferably 5, 6, or 9 ring atoms;having 6, 10, or 14 π electrons shared in a cyclic array; and having, inaddition to carbon atoms, from one to five heteroatoms. The term“heteroatom” refers to nitrogen, oxygen, or sulfur, and includes anyoxidized form of nitrogen or sulfur, and any quaternized form of a basicnitrogen. Heteroaryl groups include, without limitation, thienyl,furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl,oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl,thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl,purinyl, naphthyridinyl, benzofuranyl and pteridinyl. The terms“heteroaryl” and “heteroar-”, as used herein, also include groups inwhich a heteroaromatic ring is fused to one or more aryl,cycloaliphatic, or heterocyclyl rings, where the radical or point ofattachment is on the heteroaromatic ring. Nonlimiting examples includeindolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl,indazolyl, benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl,cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl,carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl,tetrahydroquinolinyl, tetrahydroisoquinolinyl, andpyrido[2,3-b]-1,4-oxazin-3(4H)-one. A heteroaryl group may be mono- orbicyclic. The term “heteroaryl” may be used interchangeably with theterms “heteroaryl ring”, “heteroaryl group”, or “heteroaromatic”, any ofwhich terms include rings that are optionally substituted. The term“heteroaralkyl” refers to an alkyl group substituted by a heteroaryl,wherein the alkyl and heteroaryl portions independently are optionallysubstituted. In certain embodiments, the term “5- to 10-memberedheteroaryl” refers to a 5- to 6-membered heteroaryl ring having 1 to 3heteroatoms independently selected from nitrogen, oxygen, or sulfur, oran 8- to 10-membered bicyclic heteroaryl ring having 1 to 4 heteroatomsindependently selected from nitrogen, oxygen, or sulfur. In certainembodiments, the term “5- to 12-membered heteroaryl” refers to a 5- to6-membered heteroaryl ring having 1 to 3 heteroatoms independentlyselected from nitrogen, oxygen, or sulfur, or an 8- to 12-memberedbicyclic heteroaryl ring having 1 to 4 heteroatoms independentlyselected from nitrogen, oxygen, or sulfur.

As used herein, the terms “heterocycle”, “heterocyclyl”, “heterocyclicradical”, and “heterocyclic ring” are used interchangeably and refer toa stable 5- to 7-membered monocyclic or 7-14-membered polycyclicheterocyclic moiety that is either saturated or partially unsaturated,and having, in addition to carbon atoms, one or more, preferably one tofour, heteroatoms, as defined above. When used in reference to a ringatom of a heterocycle, the term “nitrogen” includes a substitutednitrogen. As an example, in a saturated or partially unsaturated ringhaving 0-3 heteroatoms selected from oxygen, sulfur or nitrogen, thenitrogen may be N (as in 3,4-dihydro-2H-pyrrolyl), NH (as inpyrrolidinyl), or ⁺NR (as in N-substituted pyrrolidinyl). In someembodiments, the term “3- to 7-membered heterocyclic” refers to a 3- to7-membered saturated or partially unsaturated monocyclic heterocyclicring having 1 to 2 heteroatoms independently selected from nitrogen,oxygen, or sulfur. In some embodiments, the term “3- to 12-memberedheterocyclic” refers to a 3- to 8-membered saturated or partiallyunsaturated monocyclic heterocyclic ring having 1 to 2 heteroatomsindependently selected from nitrogen, oxygen, or sulfur, or a 7- to12-membered saturated or partially unsaturated polycyclic heterocyclicring having 1-3 heteroatoms independently selected from nitrogen,oxygen, or sulfur.

A heterocyclic ring can be attached to its pendant group at anyheteroatom or carbon atom that results in a stable structure and any ofthe ring atoms can be optionally substituted. Examples of such saturatedor partially unsaturated heterocyclic radicals include, withoutlimitation, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl,pyrrolidonyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl,tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl,dioxanyl, dioxolanyl, diazepinyl, oxazepinyl, thiazepinyl, morpholinyl,and quinuclidinyl. The terms “heterocycle”, “heterocyclyl”,“heterocyclyl ring”, “heterocyclic group”, “heterocyclic moiety”, and“heterocyclic radical”, are used interchangeably herein, and alsoinclude groups in which a heterocyclyl ring is fused to one or morearyl, heteroaryl, or cycloaliphatic rings, such as indolinyl,3H-indolyl, chromanyl, phenanthridinyl, or tetrahydroquinolinyl, wherethe radical or point of attachment is on the heterocyclyl ring. Aheterocyclyl group may be mono- or bicyclic. The term“heterocyclylalkyl” refers to an alkyl group substituted by aheterocyclyl, wherein the alkyl and heterocyclyl portions independentlyare optionally substituted.

As used herein, the term “partially unsaturated” refers to a ring moietythat includes at least one double or triple bond. The term “partiallyunsaturated” is intended to encompass rings having multiple sites ofunsaturation, but is not intended to include aryl or heteroarylmoieties, as herein defined.

As described herein, compounds of the invention may contain “optionallysubstituted” moieties. In general, the term “substituted”, whetherpreceded by the term “optionally” or not, means that one or morehydrogens of the designated moiety are replaced with a suitablesubstituent. Unless otherwise indicated, an “optionally substituted”group may have a suitable substituent at each substitutable position ofthe group, and when more than one position in any given structure may besubstituted with more than one substituent selected from a specifiedgroup, the substituent may be either the same or different at everyposition. Combinations of substituents envisioned by this invention arepreferably those that result in the formation of stable or chemicallyfeasible compounds. The term “stable”, as used herein, refers tocompounds that are not substantially altered when subjected toconditions to allow for their production, detection, and, in certainembodiments, their recovery, purification, and use for one or more ofthe purposes disclosed herein.

Suitable monovalent substituents on a substitutable carbon atom of an“optionally substituted” group are independently halogen;—(CH₂)₀₋₄R^(∘); —(CH₂)₀₋₄OR^(∘); —O—(CH₂)₀₋₄C(O)OR^(∘);—(CH₂)₀₋₄CH(OR^(∘))₂; —(CH₂)₀₋₄SR^(∘); —(CH₂)₀₋₄Ph, which may besubstituted with R^(∘); —(CH₂)₀₋₄O(CH₂)₀₋₁Ph which may be substitutedwith R^(∘); —CH═CHPh, which may be substituted with R^(∘); —NO₂; —CN;—N₃; —(CH₂)₀₋₄N(R^(∘))₂; —(CH₂)₀₋₄N(R^(∘))C(O)R^(∘); —N(R^(∘))C(S)R^(∘);—(CH₂)₀₋₄N(R^(∘))C(O)NR^(∘) ₂; —N(R^(∘))C(S)NR^(∘) ₂;—(CH₂)₀₋₄N(R^(∘))C(O)OR^(∘); —N(R^(∘))N(R^(∘))C(O)R^(∘);—N(R^(∘))N(R^(∘))C(O)NR^(∘) ₂; —N(R^(∘))N(R^(∘))C(O)OR^(∘);—(CH₂)₀₋₄C(O)R^(∘); —C(S)R^(∘); —(CH₂)₀₋₄C(O)OR^(∘);—(CH₂)₀₋₄C(O)N(R^(∘))₂; —(CH₂)₀₋₄C(O)SR^(∘); —(CH₂)₀₋₄C(O)OSiR^(∘) ₃;—(CH₂)₀₋₄OC(O)R^(∘); —OC(O)(CH₂)₀₋₄ SR—, SC(S)SR^(∘);—(CH₂)₀₋₄SC(O)R^(∘); —(CH₂)₀₋₄C(O)NR^(∘) ₂; —C(S)NR^(∘) ₂; —C(S)SR^(∘);—SC(S)SR^(∘), —(CH₂)₀₋₄OC(O)NR^(∘) ₂; —C(O)N(OR^(∘))R^(∘);—C(O)C(O)R^(∘); —C(O)CH₂C(O)R^(∘); —C(NOR^(∘))R^(∘); —(CH₂)₀₋₄ SSR^(∘);—(CH₂)₀₋₄S(O)₂R^(∘); —(CH₂)₀₋₄S(O)₂OR^(∘); —(CH₂)₀₋₄OS(O)₂R^(∘);—S(O)₂NR^(∘) ₂; —(CH₂)₀₋₄ S(O)R^(∘); —N(R^(∘))S(O)₂NR^(∘) ₂;—N(R^(∘))S(O)₂R^(∘); —N(OR^(∘))R^(∘); —C(NH)NR^(∘) ₂; —P(O)₂R^(∘);—P(O)R^(∘) ₂; —OP(O)R^(∘) ₂; —OP(O)(OR^(∘))₂; SiR^(∘) ₃; —(C₁₋₄ straightor branched)alkylene)O—N(R^(∘))₂; or —(C₁₋₄ straight orbranched)alkylene)C(O)O—N(R^(∘))₂, wherein each R^(∘) may be substitutedas defined below and is independently hydrogen, C₁₋₈ aliphatic, —CH₂Ph,—O(CH₂)₀₋₁Ph, or a 5-6-membered saturated, partially unsaturated, oraryl ring having 0-4 heteroatoms independently selected from nitrogen,oxygen, or sulfur, or, notwithstanding the definition above, twoindependent occurrences of R^(∘), taken together with their interveningatom(s), form a 3-12-membered saturated, partially unsaturated, or arylmono- or polycyclic ring having 0-4 heteroatoms independently selectedfrom nitrogen, oxygen, or sulfur, which may be substituted as definedbelow.

Suitable monovalent substituents on R^(∘) (or the ring formed by takingtwo independent occurrences of R^(∘) together with their interveningatoms), are independently halogen, —(CH₂)₀₋₂R^(•), -(haloR^(•)),—(CH₂)₀₋₂OH, —(CH₂)₀₋₂OR^(•), —(CH₂)₀₋₂CH(OR^(•))₂; —O(haloR^(•)), —CN,—N₃, —(CH₂)₀₋₂C(O)R^(•), —(CH₂)₀₋₂C(O)OH, —(CH₂)₀₋₂C(O)OR^(•),—(CH₂)₀₋₄C(O)N(R^(∘))₂; —(CH₂)₀₋₂SR^(•), —(CH₂)₀₋₂SH, —(CH₂)₀₋₂NH₂,—(CH₂)₀₋₂NHR^(•), —(CH₂)₀₋₂NR^(•) ₂, —NO₂, —SiR^(•) ₃, —OSiR^(•) ₃,—C(O)SR^(•), —(C₁₋₄ straight or branched alkylene)C(O)OR^(•), or—SSR^(•) wherein each R^(•) is unsubstituted or where preceded by “halo”is substituted only with one or more halogens, and is independentlyselected from C₁₋₄ aliphatic, —CH₂Ph, —O(CH₂)₀₋₁Ph, or a 5-6-memberedsaturated, partially unsaturated, or aryl ring having 0-4 heteroatomsindependently selected from nitrogen, oxygen, or sulfur. Suitabledivalent substituents on a saturated carbon atom of R^(∘) include ═O and═S.

Suitable divalent substituents on a saturated carbon atom of an“optionally substituted” group include the following: ═O, ═S, ═NNR*₂,═NNHC(O)R*, ═NNHC(O)OR*, ═NNHS(O)₂R*, ═NR*, ═NOR*, —O(C(R*₂))₂₋₃O—, or—S(C(R*₂))₂₋₃S—, wherein each independent occurrence of R* is selectedfrom hydrogen, C₁₋₆ aliphatic which may be substituted as defined below,or an unsubstituted 5-6-membered saturated, partially unsaturated, oraryl ring having 0-4 heteroatoms independently selected from nitrogen,oxygen, or sulfur. Suitable divalent substituents that are bound tovicinal substitutable carbons of an “optionally substituted” groupinclude: —O(CR*₂)₂₋₃O—, wherein each independent occurrence of R* isselected from hydrogen, C₁₋₆ aliphatic which may be substituted asdefined below, or an unsubstituted 5-6-membered saturated, partiallyunsaturated, or aryl ring having 0-4 heteroatoms independently selectedfrom nitrogen, oxygen, or sulfur.

Suitable substituents on the aliphatic group of R* include halogen,—R^(•), -(haloR^(•)), —OH, —OR^(•), —O(haloR^(•)), —CN, —C(O)OH,—C(O)OR^(•), —NH₂, —NHR^(•), —NR^(•) ₂, or —NO₂, wherein each R^(•) isunsubstituted or where preceded by “halo” is substituted only with oneor more halogens, and is independently C₁₋₄ aliphatic, —CH₂Ph,—O(CH₂)₀₋₁Ph, or a 5-6-membered saturated, partially unsaturated, oraryl ring having 0-4 heteroatoms independently selected from nitrogen,oxygen, or sulfur.

Suitable substituents on a substitutable nitrogen of an “optionallysubstituted” group include —R^(†), —NR^(†) ₂, —C(O)R^(†), —C(O)OR^(†),—C(O)C(O)R^(†), —C(O)CH₂C(O)R^(†), —S(O)₂R^(†), —S(O)₂NR^(†) ₂,—C(S)NR^(†) ₂, —C(NH)NR^(†) ₂, or —N(R^(†))S(O)₂R^(†); wherein eachR^(†) is independently hydrogen, Cis aliphatic which may be substitutedas defined below, unsubstituted —OPh, or an unsubstituted 5-6-memberedsaturated, partially unsaturated, or aryl ring having 0-4 heteroatomsindependently selected from nitrogen, oxygen, or sulfur, or,notwithstanding the definition above, two independent occurrences ofR^(†), taken together with their intervening atom(s) form anunsubstituted 3-12-membered saturated, partially unsaturated, or arylmono- or bicyclic ring having 0-4 heteroatoms independently selectedfrom nitrogen, oxygen, or sulfur.

Suitable substituents on the aliphatic group of R^(†) are independentlyhalogen, —R^(•), -(haloR^(•)), —OH, —OR^(•), —O(haloR^(•)), —CN,—C(O)OH, —C(O)OR^(•), —NH₂, —NHR^(•), —NR^(•) ₂, or —NO₂, wherein eachR^(•) is unsubstituted or where preceded by “halo” is substituted onlywith one or more halogens, and is independently C₁₋₄ aliphatic, —CH₂Ph,—O(CH₂)₀₋₁Ph, or a 5-6-membered saturated, partially unsaturated, oraryl ring having 0-4 heteroatoms independently selected from nitrogen,oxygen, or sulfur.

When substituents are described herein, the term “radical” or“optionally substituted radical” is sometimes used. In this context,“radical” means a moiety or functional group having an availableposition for attachment to the structure on which the substituent isbound. In general the point of attachment would bear a hydrogen atom ifthe substituent were an independent neutral molecule rather than asubstituent. The terms “radical” or “optionally-substituted radical” inthis context are thus interchangeable with “group” or“optionally-substituted group”.

As used herein, the “term head-to-tail” or “HT”, refers to theregiochemistry of adjacent repeating units in a polymer chain. Forexample, in the context of poly(propylene carbonate) (PPC), the termhead-to-tail based on the three regiochemical possibilities depictedbelow:

The term “head-to-tail ratio” or (H:T) refers to the proportion ofhead-to-tail linkages to the sum of all other regiochemicalpossibilities. With respect to the depiction of polymer structures,while a specific regiochemical orientation of monomer units may be shownin the representations of polymer structures herein, this is notintended to limit the polymer structures to the regiochemicalarrangement shown but is to be interpreted to encompass allregiochemical arrangements including that depicted, the oppositeregiochemistry, random mixtures, isotactic materials, syndiotacticmaterials, racemic materials, and/or enantioenriched materials andcombinations of any of these unless otherwise specified.

As used herein the term “alkoxylated” means that one or more functionalgroups on a molecule (usually the functional group is an alcohol, amine,or carboxylic acid, but is not strictly limited to these) has appendedto it a hydroxy-terminated alkyl chain. Alkoxylated compounds maycomprise a single alkyl group or they may be oligomeric moieties such ashydroxyl-terminated polyethers. Alkoxylated materials can be derivedfrom the parent compounds by treatment of the functional groups withepoxides.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a photograph of flexible foam samples prepared according toExamples 1A through 1D along with a control flexible foam sample.

FIG. 2 shows a photograph of microcellular foam samples preparedaccording to Examples 2L and 2M along with a control microcellular foamsample.

FIG. 3 shows a photograph of rigid foam samples prepared according tothe methods of Examples 3A and 3B along with a control rigid foamsample.

DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS

In one aspect, the present invention encompasses polymer compositionscomprising aliphatic polycarbonate chains cross-linked or chain extendedthrough urethane linkages. In certain embodiments, these polymercompositions comprise polyurethane foams, thermoplastics, or elastomers.

The field of polyurethane manufacture and formulation is well advanced.In some embodiments, the novel materials presented herein areformulated, processed, and used according to methods well known in theart. Combining knowledge of the art, with the disclosure and teachingsherein, the skilled artisan will readily apprehend variations,modifications and applications of the compositions, such variations arespecifically encompassed herein. The following references containinformation on the formulation, manufacture and uses of polyurethanefoams and elastomers, the entire content of each of these references isincorporated herein by reference.

-   Vahid Sendijarevic, et al.; Polymeric Foams And Foam Technology,    2^(nd) edition, Hanser Gardner Publications; 2004 (ISBN    978-1569903360)-   David Eaves; Handbook of Polymer Foams, Smithers Rapra Press; 2004    (ISBN 978-1859573884)-   Shau-Tarng Lee et al.; Polymeric Foams: Science and Technology, CRC    Press 2006 (ISBN 978-0849330759)-   Kaneyoshi Ashida; Polyurethane and Related Foams: Chemistry and    Technology, CRC Press; 2006 (ISBN 978-1587161599)-   Handbook of Thermoplastic Elastomers, William Andrew Publishers,    2007 (ISBN 978-0815515494)-   The Polyurethanes Book, J. Wiley & Sons, 2003 (ISBN 978-0470850411)

In one aspect, the polyurethane compositions of the present inventionare derived by combining two compositions: a first compositioncomprising one or more isocyanate compounds optionally containingdiluents, solvents, coreactants and the like (typically denoted the Aside mixture), and a second composition comprising one or more polyolsoptionally with additional reactants, solvents, catalysts, or additives(typically denoted the B side mixture). Before fully describing thesecompositions, the polyols and isocyanates from which they are formulatedwill be more fully described.

I. Aliphatic Polycarbonate Polyols

This section describes some of the aliphatic polycarbonate polyols thathave utility in making compositions of the present invention. In certainembodiments, compositions of the present invention comprise aliphaticpolycarbonate polyols derived from the copolymerization of one or moreepoxides and carbon dioxide. Examples of suitable polyols, as well asmethods of making them are disclosed in PCT publication WO2010/028362the entirety of which is incorporated herein by reference.

It is advantageous for many of the embodiments described herein that thealiphatic polycarbonate polyols used have a high percentage of reactiveend groups. Such reactive end-groups are typically hydroxyl groups, butother reactive functional groups may be present if the polyols aretreated to modify the chemistry of the end groups. Such modifiedmaterials may terminate in amino groups, thiol groups, alkene groups,carboxylate groups, isocyanate groups and the like. For purposes of thisinvention, the term ‘aliphatic polycarbonate polyol’ typically refers to—OH terminated materials, but also includes these end-group modifiedcompositions, unless otherwise specified.

In certain embodiments, at least 90% of the end groups of thepolycarbonate polyol used are —OH groups. In certain embodiments, atleast 95%, at least 96%, at least 97% or at least 98% of the end groupsof the polycarbonate polyol used are —OH groups. In certain embodiments,more than 99%, more than 99.5%, more than 99.7%, or more than 99.8% ofthe end groups of the polycarbonate polyol used are —OH groups. Incertain embodiments, more than 99.9% of the end groups of thepolycarbonate polyol used are —OH groups.

Another way of expressing the —OH end-group content of a polyolcomposition is by reporting its OH # which is measured using methodswell known in the art. In certain embodiments, the aliphaticpolycarbonate polyols utilized in the present invention have an OH #greater than about 40. In certain embodiments, the aliphaticpolycarbonate polyols have an OH # greater than about 50, greater thanabout 75, greater than about 100, or greater than about 120.

In certain embodiments, it is advantageous if the aliphaticpolycarbonate polyol compositions have a substantial proportion ofprimary hydroxyl end groups. These are the norm for compositionscomprising poly(ethylene carbonate), but for polyols derivedcopolymerization of substituted epoxides with CO₂, it is common for someor most of the chain ends to consist of secondary hydroxyl groups. Incertain embodiments, such polyols are treated to increase the proportionof primary —OH end groups. This may be accomplished by reacting thesecondary hydroxyl groups with reagents such as ethylene oxide, reactivelactones, and the like. In certain embodiments, the aliphaticpolycarbonate polyols are treated with beta lactones, caprolactone andthe like to introduce primary hydroxyl end groups.

In certain embodiments, aliphatic polycarbonate chains comprise acopolymer of carbon dioxide and one or more epoxides. In certainembodiments, aliphatic polycarbonate chains comprise a copolymer ofcarbon dioxide and ethylene oxide. In certain embodiments, aliphaticpolycarbonate chains comprise a copolymer of carbon dioxide andpropylene oxide. In certain embodiments, aliphatic polycarbonate chainscomprise a copolymer of carbon dioxide and cyclohexene oxide. In certainembodiments, aliphatic polycarbonate chains comprise a copolymer ofcarbon dioxide and cyclopentene oxide. In certain embodiments, aliphaticpolycarbonate chains comprise a copolymer of carbon dioxide and 3-vinylcyclohexane oxide.

In certain embodiments, aliphatic polycarbonate chains comprise aterpolymer of carbon dioxide and ethylene oxide along with one or moreadditional epoxides selected from the group consisting of propyleneoxide, 1,2-butene oxide, 2,3-butene oxide, cyclohexene oxide, 3-vinylcyclohexene oxide, epichlorohydrin, glicydyl esters, glycidyl ethers,styrene oxides, and epoxides of higher alpha olefins. In certainembodiments, such terpolymers contain a majority of repeat units derivedfrom ethylene oxide with lesser amounts of repeat units derived from oneor more additional epoxides. In certain embodiments, terpolymers containabout 50% to about 99.5% ethylene oxide-derived repeat units. In certainembodiments, terpolymers contain greater than about 60% ethyleneoxide-derived repeat units. In certain embodiments, terpolymers containgreater than 75% ethylene oxide-derived repeat units. In certainembodiments, terpolymers contain greater than 80% ethylene oxide-derivedrepeat units. In certain embodiments, terpolymers contain greater than85% ethylene oxide-derived repeat units. In certain embodiments,terpolymers contain greater than 90% ethylene oxide-derived repeatunits. In certain embodiments, terpolymers contain greater than 95%ethylene oxide-derived repeat units.

In some embodiments, aliphatic polycarbonate chains comprise a copolymerof carbon dioxide and propylene oxide along with one or more additionalepoxides selected from the group consisting of ethylene oxide,1,2-butene oxide, 2,3-butene oxide, cyclohexene oxide, 3-vinylcyclohexene oxide, epichlorohydrin, glicydyl esters, glycidyl ethers,styrene oxides, and epoxides of higher alpha olefins. In certainembodiments, such terpolymers contain a majority of repeat units derivedfrom propylene oxide with lesser amounts of repeat units derived fromone or more additional epoxides. In certain embodiments, terpolymerscontain about 50% to about 99.5% propylene oxide-derived repeat units.In certain embodiments, terpolymers contain greater than 60% propyleneoxide-derived repeat units. In certain embodiments, terpolymers containgreater than 75% propylene oxide-derived repeat units. In certainembodiments, terpolymers contain greater than 80% propyleneoxide-derived repeat units. In certain embodiments, terpolymers containgreater than 85% propylene oxide-derived repeat units. In certainembodiments, terpolymers contain greater than 90% propyleneoxide-derived repeat units. In certain embodiments, terpolymers containgreater than 95% propylene oxide-derived repeat units.

In certain embodiments, in the polymer compositions describedhereinabove, aliphatic polycarbonate chains have a number averagemolecular weight (Ms) in the range of 500 g/mol to about 250,000 g/mol.

In certain embodiments, aliphatic polycarbonate chains have an M_(n)less than about 100,000 g/mol. In certain embodiments, aliphaticpolycarbonate chains have an M_(n) less than about 70,000 g/mol. Incertain embodiments, aliphatic polycarbonate chains have an M_(n) lessthan about 50,000 g/mol. In certain embodiments, aliphatic polycarbonatechains have an M_(n) between about 500 g/mol and about 40,000 g/mol. Incertain embodiments, aliphatic polycarbonate chains have an M_(n) lessthan about 25,000 g/mol. In certain embodiments, aliphatic polycarbonatechains have an M_(n) between about 500 g/mol and about 20,000 g/mol. Incertain embodiments, aliphatic polycarbonate chains have an M_(n)between about 500 g/mol and about 10,000 g/mol. In certain embodiments,aliphatic polycarbonate chains have an M_(n) between about 500 g/mol andabout 5,000 g/mol. In certain embodiments, aliphatic polycarbonatechains have an M_(n) between about 1,000 g/mol and about 5,000 g/mol. Incertain embodiments, aliphatic polycarbonate chains have an M_(n)between about 5,000 g/mol and about 10,000 g/mol. In certainembodiments, aliphatic polycarbonate chains have an M_(n) between about500 g/mol and about 1,000 g/mol. In certain embodiments, aliphaticpolycarbonate chains have an M_(n) between about 1,000 g/mol and about3,000 g/mol. In certain embodiments, aliphatic polycarbonate chains havean M_(n) of about 5,000 g/mol. In certain embodiments, aliphaticpolycarbonate chains have an M_(n) of about 4,000 g/mol. In certainembodiments, aliphatic polycarbonate chains have an M_(n) of about 3,000g/mol. In certain embodiments, aliphatic polycarbonate chains have anM_(n) of about 2,500 g/mol. In certain embodiments, aliphaticpolycarbonate chains have an M_(n) of about 2,000 g/mol. In certainembodiments, aliphatic polycarbonate chains have an M_(n) of about 1,500g/mol. In certain embodiments, aliphatic polycarbonate chains have anM_(n) of about 1,000 g/mol.

In certain embodiments, the aliphatic polycarbonate polyols used arecharacterized in that they have a narrow molecular weight distribution.This can be indicated by the polydispersity indices (PDI) of thealiphatic polycarbonate polymers. In certain embodiments, aliphaticpolycarbonate compositions have a PDI less than 2. In certainembodiments, aliphatic polycarbonate compositions have a PDI less than1.8. In certain embodiments, aliphatic polycarbonate compositions have aPDI less than 1.5. In certain embodiments, aliphatic polycarbonatecompositions have a PDI less than 1.4. In certain embodiments, aliphaticpolycarbonate compositions have a PDI between about 1.0 and 1.2. Incertain embodiments, aliphatic polycarbonate compositions have a PDIbetween about 1.0 and 1.1.

In certain embodiments aliphatic polycarbonate compositions of thepresent invention comprise substantially alternating polymers containinga high percentage of carbonate linkages and a low content of etherlinkages. In certain embodiments, aliphatic polycarbonate compositionsof the present invention are characterized in that, on average in thecomposition, the percentage of carbonate linkages is 85% or greater. Incertain embodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that, on average in the composition, thepercentage of carbonate linkages is 90% or greater. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that, on average in the composition, thepercentage of carbonate linkages is 91% or greater. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that, on average in the composition, thepercentage of carbonate linkages is 92% or greater. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that, on average in the composition, thepercentage of carbonate linkages is 93% or greater. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that, on average in the composition, thepercentage of carbonate linkages is 94% or greater. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that, on average in the composition, thepercentage of carbonate linkages is 95% or greater. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that, on average in the composition, thepercentage of carbonate linkages is 96% or greater. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that, on average in the composition, thepercentage of carbonate linkages is 97% or greater. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that, on average in the composition, thepercentage of carbonate linkages is 98% or greater. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that, on average in the composition, thepercentage of carbonate linkages is 99% or greater. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that, on average in the composition, thepercentage of carbonate linkages is 99.5% or greater. In certainembodiments, the percentages above exclude ether linkages present inpolymerization initiators or chain transfer agents and refer only to thelinkages formed during epoxide CO₂ copolymerization.

In certain embodiments, aliphatic polycarbonate compositions of thepresent invention are characterized in that they contain essentially noether linkages either within the polymer chains derived from epoxide CO₂copolymerization or within any polymerization intiators, chain transferagents or end groups that may be present in the polymer. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that they contain, on average, less thanone ether linkage per polymer chain within the composition. In certainembodiments, aliphatic polycarbonate compositions of the presentinvention are characterized in that they contain essentially no etherlinkages.

In certain embodiments where an aliphatic polycarbonate is derived frommono-substituted epoxides (e.g. such as propylene oxide, 1,2-butyleneoxide, epichlorohydrin, epoxidized alpha olefins, or a glycidolderivative), the aliphatic polycarbonate is characterized in that it isregioregular. Regioregularity may be expressed as the percentage ofadjacent monomer units that are oriented in a head-to-tail arrangementwithin the polymer chain. In certain embodiments, aliphaticpolycarbonate chains in the inventive polymer compositions have ahead-to-tail content higher than about 80%. In certain embodiments, thehead-to-tail content is higher than about 85%. In certain embodiments,the head-to-tail content is higher than about 90%. In certainembodiments, the head-to-tail content is greater than about 91%, greaterthan about 92%, greater than about 93%, greater than about 94%, orgreater than about 95%. In certain embodiments, the head-to-tail contentof the polymer is as determined by proton or carbon-13 NMR spectroscopy.

In certain embodiments, aliphatic polycarbonate polyols useful for thepresent invention have a viscosity controlled to be within a particularrange. The preferred range may depend upon a particular application andmay be controlled to be within the normal range for a particularapplication.

In certain embodiments, where the aliphatic polycarbonate polyol is usedin the formulation of a rigid foam or a thermoplastic composition, thepolyol has a viscosity, as measured at a temperature of at least 20° C.but less than 70° C., of less than about 30,000 cps. In certainembodiments, such polyols have a viscosity less than about 20,000 cps,less than about 15,000 cps, less than about 12,000 cps, or less thanabout 10,000 cps. In certain embodiments, such polyols have a viscositybetween about 600 and about 30,000 cps. In certain embodiments, suchpolyols have a viscosity between about 2,000 and about 20,000 cps. Incertain embodiments, such polyols have a viscosity between about 5,000and about 15,000 cps.

In other embodiments, where the aliphatic polycarbonate polyol is usedin the formulation of a flexible foam, the polyol has a viscosity, asmeasured at a temperature of at least 20° C. but less than 70° C., ofless than about 10,000 cps. In certain embodiments, such polyols have aviscosity less than about 8,000 cps, less than about 6,000 cps, lessthan about 3,000 cps, or less than about 2,000 cps. In certainembodiments, such polyols have a viscosity between about 1,000 and about10,000 cps. In certain embodiments, such polyols have a viscositybetween about 1,000 and about 6,000 cps.

In certain embodiments, the polyol viscosity values described aboverepresent the viscosity as measured at 25° C. In certain embodiments,the viscosity values above represent the viscosity as measured at 30°C., 40° C., 50° C., 60° C. or 70° C.

In certain embodiments, aliphatic polycarbonate polyols useful for thepresent invention have a Tg within a particular range. The desired Tgwill vary with the application and may be controlled to be within theknown normal range for a particular application. In certain embodiments,where the polyol is used in the formulation of a flexible foam or a softelastomer composition, the polyol has a Tg less than about 20° C. Incertain embodiments, such polyols have Tg less than about 15° C., lessthan about 10° C., less than about 5° C., less than about 0° C., lessthan about −10° C., less than about −20° C., or less than about 40° C.In certain embodiments, such polyols have a Tg between about −30° C. andabout −20° C. In certain embodiments, such polyols have a Tg betweenabout −30° C. and about −20° C.

In certain embodiments, where the aliphatic polycarbonate polyol is usedin the formulation of a rigid foam or a thermoplastic composition, thepolyol has a Tg greater than about −30° C. In certain embodiments, suchpolyols have Tg greater than about −20° C., greater than about −10° C.,greater than about 0° C., greater than about 10° C., greater than about15° C., or greater than about 25° C. In certain embodiments, suchpolyols have a Tg between about −10° C. and about 30° C. In certainembodiments, such polyols have a Tg between about 0° C. and about 20° C.

In certain embodiments, compositions of the present invention comprisealiphatic polycarbonate polyols having a structure P1:

wherein,

R¹, R², R³, and R⁴ are, at each occurrence in the polymer chain,independently selected from the group consisting of —H, fluorine, anoptionally substituted C₁₋₃₀ aliphatic group, and an optionallysubstituted C₁₋₂₀ heteroaliphatic group, and an optionally substitutedC₆₋₁₀ aryl group, where any two or more of R¹, R², R³, and R⁴ mayoptionally be taken together with intervening atoms to form one or moreoptionally substituted rings optionally containing one or moreheteroatoms;

Y is, at each occurrence, independently —H or the site of attachment toany of the chain-extending moieties described in the classes andsubclasses herein;

n is at each occurrence, independently an integer from about 3 to about1,000;

is a multivalent moiety; and

x and y are each independently an integer from 0 to 6, where the sum ofx and y is between 2 and 6.

In certain embodiments, the multivalent moiety

embedded within the aliphatic polycarbonate chain is derived from apolyfunctional chain transfer agent having two or more sites from whichepoxide/CO₂ copolymerization can occur. In certain embodiments, suchcopolymerizations are performed in the presence of polyfunctional chaintransfer agents as exemplified in published PCT applicationPCT/US2009/056220 (WO/2010/028362).

In certain embodiments, a polyfunctional chain transfer agent has aformula:

wherein each of

, x, and y is as defined above and described in classes and subclassesherein.

In certain embodiments, aliphatic polycarbonate chains in the inventivepolymer compositions are derived from the copolymerization of one ormore epoxides with carbon dioxide in the presence of such polyfunctionalchain transfer agents as shown in Scheme 2:

In certain embodiments, aliphatic polycarbonate chains in polymercompositions of the present invention comprise chains with a structureP2:

wherein each of R¹, R², R³, R⁴, Y,

and n is as defined above and described in the classes and subclassesherein.

In certain embodiments where aliphatic polycarbonate chains have astructure P2,

is derived from a dihydric alcohol. In such instances

represents the carbon-containing backbone of the dihydric alcohol, whilethe two oxygen atoms adjacent to

are derived from the —OH groups of the diol. For example, if thepolyfunctional chain transfer agent were ethylene glycol, then

would be —CH₂CH₂— and P2 would have the following structure:

In certain embodiments, where

is derived from a dihydric alcohol, the dihydric alcohol comprises aC₂₋₄₀ diol. In certain embodiments, the dihydric alcohol is selectedfrom the group consisting of: 1,2-ethanediol, 1,2-propanediol,1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol,1,5-pentanediol, 2,2-dimethylpropane-1,3-diol,butyl-2-ethylpropane-1,3-diol, 2-methyl-2,4-pentane diol,2-ethyl-1,3-hexane diol, 2-methyl-1,3-propane diol, 1,5-hexanediol,1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol,2,2,4,4-tetramethylcyclobutane-1,3-diol, 1,3-cyclopentanediol,1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol,1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, isosorbide,glycerol monoesters, glycerol monoethers, trimethylolpropane monoesters,trimethylolpropane monoethers, pentaerythritol diesters, pentaerythritoldiethers, and alkoxylated derivatives of any of these.

In certain embodiments, where

is derived from a dihydric alcohol, the dihydric alcohol is selectedfrom the group consisting of: diethylene glycol, triethylene glycol,tetraethylene glycol, higher poly(ethylene glycol), such as those havingnumber average molecular weights of from 220 to about 2000 g/mol,dipropylene glycol, tripropylene glycol, and higher poly(propyleneglycols) such as those having number average molecular weights of from234 to about 2000 g/mol.

In certain embodiments, where

is derived from a dihydric alcohol, the dihydric alcohol comprises analkoxylated derivative of a compound selected from the group consistingof: a diacid, a diol, or a hydroxy acid. In certain embodiments, thealkoxylated derivatives comprise ethoxylated or propoxylated compounds.

In certain embodiments, where

is derived from a dihydric alcohol, the dihydric alcohol comprises apolymeric diol. In certain embodiments, a polymeric diol is selectedfrom the group consisting of polyethers, polyesters, hydroxy-terminatedpolyolefins, polyether-copolyesters, polyether polycarbonates,polycarbonate-copolyesters, polyoxymethylene polymers, and alkoxylatedanalogs of any of these. In certain embodiments, the polymeric diol hasan average molecular weight less than about 2000 g/mol.

In certain embodiments,

is derived from a polyhydric alcohol with more than two hydroxy groups.In certain embodiments, the aliphatic polycarbonate chains in polymercompositions of the present invention comprise aliphatic polycarbonatechains where the moiety

is derived from a triol. In certain embodiments, such aliphaticpolycarbonate chains have the structure P3:

wherein each of R¹, R², R³, R⁴, Y,

and n is as defined above and described in classes and subclassesherein.

In certain embodiments where

is derived from a triol, the triol is selected from the group consistingof: glycerol, 1,2,4-butanetriol, 2-(hydroxymethyl)-1,3-propanediol;hexane triols, trimethylol propane, trimethylol ethane,trimethylolhexane, 1,4-cyclohexanetrimethanol, pentaerythritol monoesters, pentaerythritol mono ethers, and alkoxylated analogs of any ofthese. In certain embodiments, alkoxylated derivatives compriseethoxylated or propoxylated compounds.

In certain embodiments,

is derived from an alkoxylated derivative of a trifunctional carboxylicacid or trifunctional hydroxy acid. In certain embodiments, alkoxylatedderivatives comprise ethoxylated or propoxylated compounds.

In certain embodiments, where

is derived from a polymeric triol, the polymeric triol is selected fromthe group consisting of polyethers, polyesters, hydroxy-terminatedpolyolefins, polyether-copolyesters, polyether polycarbonates,polyoxymethylene polymers, polycarbonate-copolyesters, and alkoxylatedanalogs of any of these. In certain embodiments, the alkoxylatedpolymeric triols comprise ethoxylated or propoxylated compounds.

In certain embodiments,

is derived from a polyhydric alcohol with four hydroxy groups. Incertain embodiments, aliphatic polycarbonate chains in polymercompositions of the present invention comprise aliphatic polycarbonatechains where the moiety

is derived from a tetraol. In certain embodiments, aliphaticpolycarbonate chains in polymer compositions of the present inventioncomprise chains with the structure P4:

wherein each of R¹, R², R³, R⁴, Y,

and n is as defined above and described in classes and subclassesherein.

In certain embodiments,

is derived from a polyhydric alcohol with more than four hydroxy groups.In certain embodiments,

is derived from a polyhydric alcohol with six hydroxy groups. In certainembodiments, a polyhydric alcohol is dipentaerithrotol or an alkoxylatedanalog thereof. In certain embodiments, a polyhydric alcohol is sorbitolor an alkoxylated analog thereof. In certain embodiments, aliphaticpolycarbonate chains in polymer compositions of the present inventioncomprise chains with the structure P5:

wherein each of R¹, R², R³, R⁴, Y,

and n is as defined above and described in classes and subclassesherein.

In certain embodiments, aliphatic polycarbonates of the presentinvention comprise a combination of bifunctional chains (e.g.polycarbonates of formula P2) in combination with higher functionalchains (e.g. one or more polycarbonates of formulae P3 to P5).

In certain embodiments,

is derived from a hydroxy acid. In certain embodiments, aliphaticpolycarbonate chains in polymer compositions of the present inventioncomprise chains with the structure P6:

wherein each of R¹, R², R³, R⁴, Y,

and n is as defined above and described in classes and subclassesherein. In such instances,

represents the carbon-containing backbone of the hydroxy acid, whileester and carbonate linkages adjacent to

are derived from the —CO₂H group and the hydroxy group of the hydroxyacid. For example, if

were derived from 3-hydroxy propanoic acid, then

would be —CH₂CH₂— and P6 would have the following structure:

In certain embodiments,

is derived from an optionally substituted C₂₋₄₀ hydroxy acid. In certainembodiments,

is derived from a polyester. In certain embodiments, such polyestershave a molecular weight less than about 2000 g/mol.

In certain embodiments, a hydroxy acid is an alpha-hydroxy acid. Incertain embodiments, a hydroxy acid is selected from the groupconsisting of: glycolic acid, DL-lactic acid, D-lactic acid, L-lactic,citric acid, and mandelic acid.

In certain embodiments, a hydroxy acid is a beta-hydroxy acid. Incertain embodiments, a hydroxy acid is selected from the groupconsisting of: 3-hydroxypropionic acid, DL 3-hydroxybutryic acid, D-3hydroxybutryic acid, L-3-hydroxybutyric acid, DL-3-hydroxy valeric acid,D-3-hydroxy valeric acid, L-3-hydroxy valeric acid, salicylic acid, andderivatives of salicylic acid.

In certain embodiments, a hydroxy acid is a α-ω hydroxy acid. In certainembodiments, a hydroxy acid is selected from the group consisting of: ofoptionally substituted C₃₋₂₀ aliphatic α-ω hydroxy acids and oligomericesters.

In certain embodiments, a hydroxy acid is selected from the groupconsisting of:

In certain embodiments,

is derived from a polycarboxylic acid. In certain embodiments, aliphaticpolycarbonate chains in polymer compositions of the present inventioncomprise chains with the structure P7:

wherein each of R¹, R², R₃, R⁴, Y,

and n is as defined above and described in classes and subclassesherein, and y□ is an integer from 1 to 5 inclusive.

In embodiments where the aliphatic polycarbonate chains have a structureP7,

represents the carbon-containing backbone (or a bond in the case ofoxalic acid) of a polycarboxylic acid, while ester groups adjacent to

are derived from —CO₂H groups of the polycarboxylic acid. For example,if

were derived from succinic acid (HO₂CCH₂CH₂CO₂H), then

would be —CH₂CH₂— and P7 would have the following structure:

wherein each of R¹, R², R³, R⁴, Y, and n is as defined above anddescribed in classes and subclasses herein.

In certain embodiments,

is derived from a dicarboxylic acid. In certain embodiments, aliphaticpolycarbonate chains in polymer compositions of the present inventioncomprise chains with the structure P8:

In certain embodiments,

is selected from the group consisting of: phthalic acid, isophthalicacid, terephthalic acid, maleic acid, succinic acid, malonic acid,glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaicacid.

In certain embodiments,

is selected from the group consisting of:

In certain embodiments, each

in the structures herein is independently selected from the groupconsisting of:

-   wherein each R^(x) is independently an optionally substituted group    selected from the group consisting of C₂₋₂₀ aliphatic, C₂₋₂₀    heteroaliphatic, 3- to 14-membered carbocyclic, 6- to 10-membered    aryl, 5- to 10-membered heteroaryl, and 3- to 12-membered    heterocyclic.

In certain embodiments, each

in the structures herein is independently selected from the groupconsisting of:

wherein R^(x) is as defined above and described in classes andsubclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise:

-   -   wherein each of        , —Y, and n is as defined above and described in classes and        subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of —Y and n is as defined above and described in        classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of —Y and n is as defined above and described in        classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of —Y and n is as defined above and described in        classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of —Y and n is as defined above and described in        classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of        , —Y, and n is as defined above and described in classes and        subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of —Y and n is as defined above and described in        classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of —Y and n is as defined above and described in        classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of —Y and n is as defined above and described in        classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of        , —Y, and n is as defined above and described in classes and        subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of —Y and n are is as defined above and described        in classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of        , —Y, and n is as defined above and described in classes and        subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of —Y and n is as defined above and described in        classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of        , —Y, and n is as defined above and described in classes and        subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of —Y and n is as defined above and described in        classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of        , —Y, R^(x), and n is as defined above and described in classes        and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of —Y, R^(x), and n is as defined above and        described in classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of        , —Y, and n is as defined above and described in classes and        subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of        , —Y, and n are is as defined above and described in classes and        subclasses herein; and each        independently represents a single or double bond.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of —Y and n is as defined above and described in        classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of —Y,        , and n is as defined above and described in classes and        subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of        , R^(x), —Y and n is as defined above and described in classes        and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of —Y, R^(x), and n is as defined above and        described in classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of        , —Y, and n is as defined above and described in classes and        subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of —Y,        , and n is as defined above and described in classes and        subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of —Y and n is as defined above and described in        classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of —Y,        , and n is as defined above and described in classes and        subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of        , —Y, and n is as defined above and described in classes and        subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

-   -   wherein each of —Y and n is as defined above and described in        classes and subclasses herein.

In certain embodiments, in polycarbonates of structures P2a, P2c, P2d,P2f, P2h, P2j, P2l, P2l-a, P2n, P2p, and P2r,

is selected from the group consisting of: ethylene glycol; diethyleneglycol, triethylene glycol, 1,3 propane diol; 1,4 butane diol, hexyleneglycol, 1,6 hexane diol, propylene glycol, dipropylene glycol,tripopylene glycol, and alkoxylated derivatives of any of these.

For polycarbonates comprising repeat units derived from two or moreepoxides, such as those represented by structures P2f through P2r,depicted above, it is to be understood that the structures drawn mayrepresent mixtures of positional isomers or regioisomers that are notexplicitly depicted. For example, the polymer repeat unit adjacent toeither end group of the polycarbonate chains can be derived from eitherone of the two epoxides comprising the copolymers. Thus, while thepolymers may be drawn with a particular repeat unit attached to an endgroup, the terminal repeat units might be derived from either of the twoepoxides and a given polymer composition might comprise a mixture of allof the possibilities in varying ratios. The ratio of these end-groupscan be influenced by several factors including the ratio of the differrent epoxides used in the polymerization, the structure of the catalystused, the reaction conditions used (i.e temperature pressure, etc.) aswell as by the timing of addition of reaction components. Similarly,while the drawings above may show a defined regiochemistry for repeatunits derived from substituted epoxides, the polymer compositions will,in some cases, contain mixtures of regioisomers. The regioselectivity ofa given polymerization can be influenced by numerous factors includingthe structure of the catalyst used and the reaction conditions employed.To clarify, this means that the composition represented by structure P2rabove, may contain a mixture of several compounds as shown in thediagram below. This diagram shows the isomers graphically for polymerP2r, where the structures below the depiction of the chain show eachregio- and positional isomer possible for the monomer unit adjacent tothe chain transfer agent and the end groups on each side of the mainpolymer chain. Each end group on the polymer may be independentlyselected from the groups shown on the left or right while the centralportion of the polymer including the chain transfer agent and its twoadjacent monomer units may be independently selected from the groupsshown. In certain embodiments, the polymer composition comprises amixture of all possible combinations of these. In other embodiments, thepolymer composition is enriched in one or more of these.

In certain embodiments, the aliphatic polycarbonate polyol is selectedfrom the group consisting of Q1, Q2, Q3, Q4, Q5, Q6, and mixtures of anytwo or more of these.

-   -   wherein, t is an integer from 1 to 12 inclusive, and R^(t) is        independently at each occurrence —H, or —CH₃.

In certain embodiments, the aliphatic polycarbonate polyol is selectedfrom the group consisting of:

Poly(ethylene carbonate) of formula Q1 having an average molecularweight number of between about 500 g/mol and about 3,000 g/mol, apolydisperisty index less than about 1.25, at least 85% carbonatelinkages, and at least 98% —OH end groups;

Poly(ethylene carbonate) of formula Q1 having an average molecularweight number of about 500 g/mol, a polydisperisty index less than about1.25, at least 85% carbonate linkages, and at least 98% —OH end groups;

Poly(ethylene carbonate) of formula Q1 having an average molecularweight number of about 1,000 g/mol, a polydisperisty index less thanabout 1.25, at least 85% carbonate linkages, and at least 98% —OH endgroups;

Poly(ethylene carbonate) of formula Q1 having an average molecularweight number of about 2,000 g/mol, a polydisperisty index less thanabout 1.25, at least 85% carbonate linkages, and at least 98% —OH endgroups;

Poly(ethylene carbonate) of formula Q1 having an average molecularweight number of about 3,000 g/mol, a polydisperisty index less thanabout 1.25, at least 85% carbonate linkages, and at least 98% —OH endgroups;

Poly(propylene carbonate) of formula Q2 having an average molecularweight number of between about 500 g/mol and about 3,000 g/mol, apolydisperisty index less than about 1.25, at least 95% carbonatelinkages, and at least 98% —OH end groups;

Poly(propylene carbonate) of formula Q2 having an average molecularweight number of about 500 g/mol, a polydisperisty index less than about1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;

Poly(propylene carbonate) of formula Q2 having an average molecularweight number of about 1,000 g/mol, a polydisperisty index less thanabout 1.25, at least 95% carbonate linkages, and at least 98% —OH endgroups;

Poly(propylene carbonate) of formula Q2 having an average molecularweight number of about 2,000 g/mol, a polydisperisty index less thanabout 1.25, at least 95% carbonate linkages, and at least 98% —OH endgroups;

Poly(propylene carbonate) of formula Q2 having an average molecularweight number of about 3,000 g/mol, a polydisperisty index less thanabout 1.25, at least 95% carbonate linkages, and at least 98% —OH endgroups;

Poly(ethylene-co-propylene carbonate) of formula Q3 having an averagemolecular weight number of between about 500 g/mol and about 3,000g/mol, a polydisperisty index less than about 1.25, at least 90%carbonate linkages, and at least 98% —OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q3 having an averagemolecular weight number of about 500 g/mol, a polydisperisty index lessthan about 1.25, at least 90% carbonate linkages, and at least 98% —OHend groups;

Poly(ethylene-co-propylene carbonate) of formula Q3 having an averagemolecular weight number of about 1,000 g/mol, a polydisperisty indexless than about 1.25, at least 90% carbonate linkages, and at least 98%—OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q3 having an averagemolecular weight number of about 2,000 g/mol (e.g. n is on averagebetween about 10 and about 11), a polydisperisty index less than about1.25, at least 90% carbonate linkages, and at least 98% —OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q3 having an averagemolecular weight number of about 3,000 g/mol, a polydisperisty indexless than about 1.25, at least 95% carbonate linkages, and at least 98%—OH end groups;

Poly(ethylene carbonate) of formula Q4 having an average molecularweight number of between about 500 g/mol and about 3,000 g/mol (e.g.each n is between about 4 and about 16), a polydisperisty index lessthan about 1.25, at least 95% carbonate linkages, and at least 98% —OHend groups;

Poly(ethylene carbonate) of formula Q4 having an average molecularweight number of about 500 g/mol, a polydisperisty index less than about1.25, at least 85% carbonate linkages, and at least 98% —OH end groups;

Poly(ethylene carbonate) of formula Q4 having an average molecularweight number of about 1,000 g/mol, a polydisperisty index less thanabout 1.25, at least 85% carbonate linkages, and at least 98% —OH endgroups;

Poly(ethylene carbonate) of formula Q4 having an average molecularweight number of about 2,000 g/mol, a polydisperisty index less thanabout 1.25, at least 85% carbonate linkages, and at least 98% —OH endgroups;

Poly(ethylene carbonate) of formula Q4 having an average molecularweight number of about 3,000 g/mol, a polydisperisty index less thanabout 1.25, at least 85% carbonate linkages, and at least 98% —OH endgroups.

Poly(propylene carbonate) of formula Q5 having an average molecularweight number of between about 500 g/mol and about 3,000 g/mol, apolydisperisty index less than about 1.25, at least 95% carbonatelinkages, and at least 98% —OH end groups;

Poly(propylene carbonate) of formula Q5 having an average molecularweight number of about 500 g/mol, a polydisperisty index less than about1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;

Poly(propylene carbonate) of formula Q5 having an average molecularweight number of about 1,000 g/mol, a polydisperisty index less thanabout 1.25, at least 95% carbonate linkages, and at least 98% —OH endgroups;

Poly(propylene carbonate) of formula Q5 having an average molecularweight number of about 2,000 g/mol, a polydisperisty index less thanabout 1.25, at least 95% carbonate linkages, and at least 98% —OH endgroups;

Poly(propylene carbonate) of formula Q5 having an average molecularweight number of about 3,000 g/mol, a polydisperisty index less thanabout 1.25, at least 95% carbonate linkages, and at least 98% —OH endgroups;

Poly(ethylene-co-propylene carbonate) of formula Q6 having an averagemolecular weight number of between about 500 g/mol and about 3,000g/mol, a polydisperisty index less than about 1.25, at least 90%carbonate linkages, and at least 98% —OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q6 having an averagemolecular weight number of about 500 g/mol, a polydisperisty index lessthan about 1.25, at least 90% carbonate linkages, and at least 98% —OHend groups;

Poly(ethylene-co-propylene carbonate) of formula Q6 having an averagemolecular weight number of about 1,000 g/mol, a polydisperisty indexless than about 1.25, at least 90% carbonate linkages, and at least 98%—OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q6 having an averagemolecular weight number of about 2,000 g/mol (e.g. n is on averagebetween about 10 and about 11), a polydisperisty index less than about1.25, at least 90% carbonate linkages, and at least 98% —OH end groups;and

Poly(ethylene-co-propylene carbonate) of formula Q6 having an averagemolecular weight number of about 3,000 g/mol, a polydisperisty indexless than about 1.25, at least 95% carbonate linkages, and at least 98%—OH end groups.

In certain embodiments, the embedded chain transfer agent

is a moiety derived from a polymeric diol or higher polyhydric alcohol.In certain embodiments, such polymeric alcohols are polyether orpolyester polyols. In certain embodiments

is a polyether polyol comprising ethylene glycol or propylene glycolrepeating units (—OCH₂CH₂O—, or —OCH₂CH(CH₃)O—) or combinations ofthese. In certain embodiments,

is a polyester polyol comprising the reaction product of a diol and adiacid, or a material derived from ring-opening polymerization oflactones.

In certain embodiments where

comprises a polyether diol, the aliphatic polycarbonate polyol has astructure Q7:

wherein,

R^(q) is at each occurrence in the polymer chain independently —H or—CH₃;

R^(a) is —H, or —CH₃;

q and q′ are independently an integer from about 2 to about 40; and

and n is as defined above and in the examples and embodiments herein.

In certain embodiments, an aliphatic polycarbonate polyol is selectedfrom the group consisting of:

-   -   wherein each of R^(a), R^(q), q, q′, and n is as defined above        and described in classes and subclasses herein.

In certain embodiments, where aliphatic polycarbonate polyols comprisecompounds conforming to structure Q7, the moiety

is derived from a commercially available polyether polyol such as thosetypically used in the formulation of polyurethane foam compositions.

In certain embodiments where

comprises a polyester diol, the aliphatic polycarbonate polyol has astructure Q8:

-   -   wherein,    -   c is at each occurrence in the polymer chain independently an        integer from 0 to 6;    -   d is at each occurrence in the polymer chain independently an        integer from 1 to 11; and    -   each of R^(q), n, q, and q′ is as defined above and described in        classes and subclasses herein.

In certain embodiments, an aliphatic polycarbonate polyol is selectedfrom the group consisting of:

-   -   wherein each of n and q is as defined above and described in        classes and subclasses herein.

In certain embodiments, where aliphatic polycarbonate polyols comprisecompounds conforming to structure Q8, the moiety

is derived from a commercially available polyester polyol such as thosetypically used in the formulation of polyurethane foam compositions.

II. Isocyanate Reagents

As described above, the compositions of the present invention compriseisocyanate reagents. The purpose of these isocyanate reagents is toreact with the reactive end groups on the aliphatic polycarbonatepolyols to form higher molecular weight structures through chainextension and/or cross-linking.

The art of polyurethane synthesis is well advanced and a very largenumber of isocyanates and related polyurethane precursors are known inthe art and available commercially. While this section of thespecification describes isocyanates suitable for use in certainembodiments of the present invention, it is to be understood that it iswithin the capabilities of one skilled in the art of polyurethaneformulation to use alternative isocyanates along with the teachings ofthis disclosure to formulate additional compositions of matter withinthe scope of the present invention. Descriptions of suitable isocyanatecompounds and related methods can be found in: Chemistry and Technologyof Polyols for Polyurethanes Ionescu, Mihail 2005 (ISBN978-1-84735-035-0), and H. Ulrich, “Urethane Polymers,” Kirk-OthmerEncyclopedia of Chemical Technology, 1997 the entirety of each of whichis incorporated herein by reference.

In certain embodiments, the isocyanate reagents comprise two or moreisocyanate groups per molecule. In certain embodiments the isocyanatereagents are diisocyanates. In other embodiments, the isocyanatereagents are higher polyisocyanates such as triisocyanates,tetraisocyanates, isocyanate polymers or oligomers, and the like. Incertain embodiments, the isocyanate reagents are aliphaticpolyisocyanates or derivatives or oligomers of aliphaticpolyisocyanates. In other embodiments, the isocyanates are aromaticpolyisocyanates or derivatives or oligomers of aromatic polyisocyanates.In certain embodiments, the compositions may comprise mixtures of anytwo or more of the above types of isocyanates.

In certain embodiments, the isocyanate component used in the formulationof the novel materials of the present invention have a functionality of2 or more. In certain embodiments, the isocyanate component of theinventive materials comprise a mixture of diisocyanates and higherisocyanates formulated to achieve a particular functionality number fora given application. In certain embodiments, where the inventivecomposition is a flexible foam or a soft elastomer, the isocyanateemployed has a functionality of about 2. In certain embodiments, suchisocyanates have a functionality between about 2 and about 2.7. Incertain embodiments, such isocyanates have a functionality between about2 and about 2.5. In certain embodiments, such isocyanates have afunctionality between about 2 and about 2.3. In certain embodiments,such isocyanates have a functionality between about 2 and about 2.2.

In other embodiments, where the inventive composition is a rigid foam ora thermoplastic, the isocyanate employed has a functionality greaterthan 2. In certain embodiments, such isocyanates have a functionalitybetween about 2.3 and about 4. In certain embodiments, such isocyanateshave a functionality between about 2.5 and about 3.5. In certainembodiments, such isocyanates have a functionality between about 2.6 andabout 3.1. In certain embodiments, such isocyanates have a functionalityof about 3.

In certain embodiments, an isocyanate reagent is selected from the groupconsisting of: 1,6-hexamethylaminediisocyanate (HDI), isophoronediisocyanate (IPDI), 4,4□methylene-bis(cyclohexyl isocyanate) (H₁₂MDI),2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate (TDI),diphenylmethane-4,4

diisocyanate (MDI), diphenylmethane-2,4

diisocyanate (MDI), xylylene diisocyanate (XDI),1,3-Bis(isocyanatomethyl)cyclohexane (H6-XDI),2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylenediisocyanate (TMDI), m-tetramethylxylylene diisocyanate (TMXDI),p-tetramethylxylylene diisocyanate (TMXDI), isocyanatomethyl-1,8-ictanediisocyanate (TIN), triphenylmethane-4,4′,4″triisocyanate,Tris(p-isocyanatomethyl)thiosulfate, 1,3-Bis(isocyanatomethyl)benzene,1,4-tetramethylene diisocyanate, trimethylhexane diisocyanate,1,6-hexamethylene diisocyanate, 1,4-cyclohexyl diisocyanate, lysinediisocyanate, and mixtures of any two or more of these.

Isocyanates suitable for certain embodiments of the present inventionare available commercially under various trade names. Examples ofsuitable commercially available isocyanates include materials sold undertrade names: Desmodur® (Bayer Material Science), Tolonate® (Perstorp),Takenate® (Takeda), Vestanat® (Evonik), Desmotherm® (Bayer MaterialScience), Bayhydur® (Bayer Material Science), Mondur (Bayer MaterialScience), Suprasec (Huntsman Inc.), Lupranate® (BASF), Trixene(Baxenden), Hartben® (Benasedo), Ucopol® (Sapici), and Basonat® (BASF).Each of these trade names encompasses a variety of isocyanate materialsavailable in various grades and formulations. The selection of suitablecommercially-available isocyanate materials as reagents to producepolyurethane compositions for a particular application is within thecapability of one skilled in the art of polyurethane technology usingthe teachings and disclosure of this patent application along with theinformation provided in the product data sheets supplied by theabove-mentioned suppliers.

Additional isocyanates suitable for certain embodiments of the presentinvention are sold under the trade name Lupranate® (BASF). In certainembodiments, the isocyanates are selected from the group consisting ofthe materials shown in Table 1:

TABLE 1 Nominal Products Description % NCO Funct. Lupranate M 4,4′ MDI33.5 2 Lupranate MS 4,4′ MDI 33.5 2 Lupranate MI 2,4′ and 4,4′ MDI Blend33.5 2 Lupranate LP30 Liquid Pure 4,4′ MDI 33.1 2 Lupranate 227Monomeric/Modified MDI 32.1 2 Blend Carbodiimide Modified MDI Lupranate5143 Carbodiimide Modified 29.2 2.2 4,4′ MDI Lupranate CarbodiimideModified 29.5 2.2 MM103 4,4′ MDI Lupranate 219 Carbodiimide Modified29.2 2.2 4,4′ MDI Lupranate 81 Carbodiimide Modified MDI 29.5 2.2Lupranate 218 Carbodiimide Modified MDI 29.5 2.2 Polymeric MDI (PMDI)Lupranate M10 Low Funct. Polymeric 31.7 2.2 Lupranate Polymeric MDIVariant 31.5 2.7 R2500U Lupranate M20S Mid-Functionality Polymeric 31.52.7 Lupranate Mid-Functionality Polymeric 31.5 2.7 M20FB Lupranate M70LHigh-Functionality Polymeric 31 3 Lupranate M200 High-FunctionalityPolymeric 30 3.1 Polymeric MDI Blends and Derivatives Lupranate 241 LowFunctionality Polymeric 32.6 2.3 Lupranate 230 Low Viscosity Polymeric32.5 2.3 Lupranate 245 Low Viscosity Polymeric 32.3 2.3 Lupranate MidFunctionality Polymeric 32.3 2.4 TF2115 Lupranate 78 Mid FunctionalityPolymeric 32 2.3 Lupranate 234 Low Functionality Polymeric 32 2.4Lupranate 273 Low Viscosity Polymeric 32 2.5 Lupranate 266 Low ViscosityPolymeric 32 2.5 Lupranate 261 Low Viscosity Polymeric 32 2.5 Lupranate255 Low Viscosity Polymeric 31.9 2.5 Lupranate 268 Low ViscosityPolymeric 30.6 2.4 Select MDI Prepolymers Lupranate 5010 HigherFunctional Prepolymer 28.6 2.3 Lupranate 223 Low Visc. Derivative ofPure 27.5 2.2 MDI Lupranate 5040 Mid Functional, Low Viscosity 26.3 2.1Lupranate 5110 Polymeric MDI Prepolymer 25.4 2.3 Lupranate MP102 4,4′MDI Prepolymer 23 2 Lupranate 5090 Special 4,4′ MDI Prepolymer 23 2.1Lupranate 5050 Mid Functional, Mid NCO 21.5 2.1 Prepol Lupranate 5030Special MDI Prepolymer 18.9 NA Lupranate 5080 2,4′-MDI EnhancedPrepolymer 15.9 2 Lupranate 5060 Low Funct, Higher MW Prepol 15.5 2Lupranate 279 Low Funct, Special Prepolymer 14 2 Lupranate 5070 SpecialMDI Prepolymer 13 2 Lupranate 5020 Low Functionality, Low NCO 9.5 2Toluene Diisocyanate (TDI) Lupranate T80- 80/20:2,4/2,6 TDI 48.3 2Lupranate T80- High Acidity TDI 48.3 2 Lupranate 802080/20:TDI/Polymeric MDI 44.6 2.1

Other isocyanates suitable for certain embodiments of the presentinvention are sold under the trade name Desmondur® available from BayerMaterial Science. In certain embodiments, the isocyanates are selectedfrom the group consisting of the materials shown in Table 2:

TABLE 2 Trade Name Description Desmodur ® 2460 M Monomericdiphenylmethane diisocyanate with high 2,4

isomer content Desmodur ® 44 M A monomeric diphenylmethane-4,4

diisocyanate (MDI). Desmodur ® 44 MC Desmodur 44 MC Flakes is amonomeric diphenylmethane-4,4

diisocyanate (MDI). Desmodur ® BL 1100/1 Blocked aromatic polyisocyanatebased on TDI Desmodur ® BL 1265 Blocked aromatic polyisocyanate based onTDI MPA/X Desmodur ® BL 3175 SN Blocked, aliphatic polyisocyanate basedon HDI Desmodur ® BL 3272 MPA Blocked aliphatic polyisocyanate based onHDI Desmodur ® BL 3370 MPA Blocked aliphatic polyisocyanate based on HDIDesmodur ® BL 3475 Aliphatic crosslinking stoving urethane resin basedon HDI/IPDI BA/SN Desmodur ® BL 3575/1 Blocked aliphatic polyisocyanatebased on HDI MPA/SN Desmodur ® BL 4265 SN Blocked, aliphaticpolyisocyanate based on IPDI Desmodur ® BL 5375 Blocked aliphaticpolyisocyanate based on H 12 MDI Desmodur ® CD-L Desmodur CD-L is amodified isocyanate based on diphenylmethane- 4,4

diisocyanate. Desmodur ® CD-S Desmodur CD-S is a modified isocyanatebased on diphenylmethane- 4,4

diisocyanate. Desmodur ® D XP 2725 Hydrophilically modifiedpolyisocyanate Desmodur ® DA-L Hydrophilic aliphatic polyisocyanatebased on hexamethylene diisocyanate Desmodur ® DN Aliphaticpolyisocyanate of low volatility Desmodur ® E 1160 Aromaticpolyisocyanate prepolymer based on toluene diisocyanate Desmodur ® E1361 BA Aromatic polyisocyanate prepolymer based on toluylenediisocyanate Desmodur ® E 1361 Aromatic polyisocyanate prepolymer basedon toluene diisocyanate MPA/X Desmodur ® E 14 Aromatic polyisocyanateprepolymer based on toluene diisocyanate Desmodur ® E 15 Aromaticpolyisocyanate prepolymer based on toluene diisocyanate. Desmodur ® E1660 Aromatic polyisocyanate prepolymer based on toluene diisocyanate.Desmodur ® E 1750 PR Polyisocyanate prepolymer based on toluenediisocyanate Desmodur ® E 20100 Modified polyisocyanate prepolymer basedon diphenylmethane diisocyanate. Desmodur ® E 21 Aromatic polyisocyanateprepolymer based on diphenylmethane diisocyanate (MDI). Desmodur ® E2190 X Aromatic polyisocyanate prepolymer based on diphenylmethanediisocyanate (MDI) Desmodur ® E 22 Aromatic polyisocyanate prepolymerbased on diphenylmethane diisocyanate. Desmodur ® E 2200/76 Desmodur E2200/76 is a prepolymer based on (MDI) with isomers. Desmodur ® E 23Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate(MDI). Desmodur ® E 29 Polyisocyanate prepolymer based ondiphenylmethane diisocyanate. Desmodur ® E 305 Desmodur E 305 is alargely linear aliphatic NCO prepolymer based on hexamethylenediisocyanate. Desmodur ® E 3265 Aliphatic polyisocyanate prepolymerbased on hexamethylene MPA/SN diisocyanate (HDI) Desmodur ® E 3370Aliphatic polyisocyanate prepolymer based on hexamethylene diisocyanateDesmodur ® E XP 2605 Polyisocyanate prepolymer based on toluenediisocyanate and diphenylmethan diisocyanate Desmodur ® E XP 2605Polyisocyanate prepolymer based on toluene diisocyanate anddiphenylmethan diisocyanate Desmodur ® E XP 2715 Aromatic polyisocyanateprepolymer based on 2,4

diphenylmethane diisocyanate (2,4

MDI) and a hexanediol adipate Desmodur ® E XP 2723 Aromaticpolyisocyanate prepolymer based on diphenylmethane diisocyanate (MDI).Desmodur ® E XP 2726 Aromatic polyisocyanate prepolymer based on 2,4

diphenylmethane diisocyanate (2,4

MDI) Desmodur ® E XP 2727 Aromatic polyisocyanate prepolymer based ondiphenylmethane diisocyanate. Desmodur ® E XP 2762 Aromaticpolyisocyanate prepolymer based on diphenylmethane diisocyanate (MDI).Desmodur ® H Monomeric aliphatic diisocyanate Desmodur ® HLAromatic/aliphatic polyisocyanate based on toluylene diisocyanate/hexamethylene diisocyanate Desmodur ® I Monomeric cycloaliphaticdiisocyanate. Desmodur ® IL 1351 Aromatic polyisocyanate based ontoluene diisocyanate Desmodur ® IL 1451 Aromatic polyisocyanate based ontoluene diisocyanate Desmodur ® IL BA Aromatic polyisocyanate based ontoluene diisocyanate Desmodur ® IL EA Aromatic polyisocyante resin basedon toluylene diisocyanate Desmodur ® L 1470 Aromatic polyisocyanatebased on toluene diisocyanate Desmodur ® L 67 BA Aromatic polyisocyanatebased on tolulene diisocyanate Desmodur ® L 67 MPA/X Aromaticpolyisocyanate based on tolulene diisocyanate Desmodur ® L 75 Aromaticpolyisocyanate based on tolulene diisocyanate Desmodur ® LDLow-functionality isocyanate based on hexamethylene diisocyanate (HDI)Desmodur ® LS 2424 Monomeric diphenylmethane diisocyanate with high 2,4

isomer content Desmodur ® MT Polyisocyanate prepolymer based ondiphenylmethane diisocyanate Desmodur ® N 100 Aliphatic polyisocyanate(HDI biuret) Desmodur ® N 3200 Aliphatic polyisocyanate (low-viscosityHDI biuret) Desmodur ® N 3300 Aliphatic polyisocyanate (HDI trimer)Desmodur ® N 3368 BA/SN Aliphatic polyisocyanate (HDI trimer) Desmodur ®N 3368 SN Aliphatic polyisocyanate (HDI trimer) Desmodur ® N 3386 BA/SNAliphatic polyisocyanate (HDI trimer) Desmodur ® N 3390 BA Aliphaticpolyisocyanate (HDI trimer) Desmodur ® N 3390 BA/SN Aliphaticpolyisocyanate (HDI trimer) Desmodur ® N 3400 Aliphatic polyisocyanate(HDI uretdione) Desmodur ® N 3600 Aliphatic polyisocyanate(low-viscosity HDI trimer) Desmodur ® N 3790 BA Aliphatic polyisocyanate(high functional HDI trimer) Desmodur ® N 3800 Aliphatic polyisocyanate(flexibilizing HDI trimer) Desmodur ® N 3900 Low-viscosity, aliphaticpolyisocyanate resin based on hexamethylene diisocyanate Desmodur ® N 50BA/MPA Aliphatic polyisocyanate (HDI biuret) Desmodur ® N 75 BAAliphatic polyisocyanate (HDI biuret) Desmodur ® N 75 MPA Aliphaticpolyisocyanate (HDI biuret) Desmodur ® N 75 MPA/X Aliphaticpolyisocyanate (HDI biuret) Desmodur ® NZ 1 Aliphatic polyisocyanateDesmodur ® PC-N Desmodur PC-N is a modified diphenyl-methane-4,4

diisocyanate (MDI). Desmodur ® PF Desmodur PF is a modifieddiphenyl-methane-4,4

diisocyanate (MDI). Desmodur ® PL 340, 60% Blocked aliphaticpolyisocyanate based on IPDI BA/SN Desmodur ® PL 350 Blocked aliphaticpolyisocyanate based on HDI Desmodur ® RC Solution of a polyisocyanurateof toluene diisocyanate (TDI) in ethyl acetate. Desmodur ® RE Solutionof triphenylmethane-4,4,

triisocyanate in ethyl acetate Desmodur ® RFE Solution oftris(p-isocyanatophenyl) thiophosphate in ethyl acetate Desmodur ® RNSolution of a polyisocyanurate with aliphatic and aromatic NCO groups inethyl acetate. Desmodur ® T 100 Pure 2,4′-toluene diisocyanate (TDI)Desmodur ® T 65 N 2,4- and 2,6-toluene diisocyanate (TDI) in the ratio67:33 Desmodur ® T 80 2,4- and 2,6-toluene diisocyanate (TDI) in theratio 80:20 Desmodur ® T 80 P 2,4- and 2,6-toluene diisocyanate (TDI) inthe ratio 80:20 with an increased content of hydrolysable chlorineDesmodur ® VH 20 N Polyisocyanate based on diphenylmethane diisocyanateDesmodur ® VK Desmodur VK products re mixtures of diphenylmethane-4,4

diisocyanate (MDI) with isomers and higher functional homologuesDesmodur ® VKP 79 Desmodur VKP 79 is a modified diphenylmethane-4,4

diisocyanate (MDI) with isomers and homologues. Desmodur ® VKS 10Desmodur VKS 10 is a mixture of diphenylmethane-4,4

diisocyanate (MDI) with isomers and higher functional homologues (PMDI).Desmodur ® VKS 20 Desmodur VKS 20 is a mixture of diphenylmethane-4,4

diisocyanate (MDI) with isomers and higher functional homologues (PMDI).Desmodur ® VKS 20 F Desmodur VKS 20 F is a mixture ofdiphenylmethane-4,4

diisocyanate (MDI) with isomers and higher functional homologuesDesmodur ® VKS 70 Desmodur VKS 70 is a mixture of diphenylmethane-4,4

diisocyanate (MDI) with isomers and homologues. Desmodur ® VL Aromaticpolyisocyanate based on diphenylmethane diisocyanate Desmodur ® VP LS2078/2 Blocked aliphatic polyisocyanate based on IPDI Desmodur ® VP LS2086 Aromatic polyisocyanate prepolymer based on diphenylmethanediisocyanate Desmodur ® VP LS 2257 Blocked aliphatic polyisocyanatebased on HDI Desmodur ® VP LS 2371 Aliphatic polyisocyanate prepolymerbased on isophorone diisocyanate. Desmodur ® VP LS 2397 Desmodur VP LS2397 is a linear prepolymer based on polypropylene ether glycol anddiphenylmethane diisocyanate (MDI). Desmodur ® W Monomericcycloaliphatic diisocyanate Desmodur ® W/1 Monomeric cycloaliphaticdiisocyanate Desmodur ® XP 2404 Desmodur XP 2404 is a mixture ofmonomeric polyisocyanates Desmodur ® XP 2406 Aliphatic polyisocyanateprepolymer based on isophorone diisocyanate Desmodur ® XP 2489 Aliphaticpolyisocyanate Desmodur ® XP 2505 Desmodur XP 2505 is a prepolymercontaining ether groups based on diphenylmethane-4,4′-diisocyanates(MDI) Desmodur ® XP 2551 Aromatic polyisocyanate based ondiphenylmethane diisocyanate Desmodur ® XP 2565 Low-viscosity, aliphaticpolyisocyanate resin based on isophorone diisocyanate. Desmodur ® XP2580 Aliphatic polyisocyanate based on hexamethylene diisocyanateDesmodur ® XP 2599 Aliphatic prepolymer containing ether groups andbased on hexamethylene-1,6-diisocyanate (HDI) Desmodur ® XP 2617Desmodur XP 2617 is a largely linear NCO prepolymer based onhexamethylene diisocyanate. Desmodur ® XP 2665 Aromatic polyisocyanateprepolymer based on diphenylmethane diisocyanate (MDI). Desmodur ® XP2675 Aliphatic polyisocyanate (highly functional HDI trimer) Desmodur ®XP 2679 Aliphatic polyisocyanate (HDI allophanate trimer) Desmodur ® XP2714 Silane-functional aliphatic polyisocyanate based on hexamethylenediisocyanate Desmodur ® XP 2730 Low-viscosity, aliphatic polyisocyanate(HDI uretdione) Desmodur ® XP 2731 Aliphatic polyisocyanate (HDIallophanate trimer) Desmodur ® XP 2742 Modified aliphatic Polyisocyanate(HDI-Trimer), contains SiO2- nanoparticles

Additional isocyanates suitable for certain embodiments of the presentinvention are sold under the trade name Tolonate® (Perstorp). In certainembodiments, the isocyanates are selected from the group consisting ofthe materials shown in Table 3:

TABLE 3 Tolonate ™ D2 a blocked aliphatic polyisocyanate, supplied at75% solids in aromatic solvent Tolonate ™ HDB a viscous solvent-freealiphatic polyisocyanate Tolonate ™ HDB-LV a solvent free low viscosityaliphatic polyisocyanate Tolonate ™ HDB 75 B an aliphaticpolyisocyanate, supplied at 75% solids in methoxy propyl acetateTolonate ™ HDB 75 BX an aliphatic polyisocyanate, supplied at 75% solidsTolonate ™ HDT a medium viscosity, solvent-free aliphatic polyisocyanateTolonate ™ HDT-LV is a solvent free low viscosity aliphaticpolyisocyanate Tolonate ™ HDT-LV2 a solvent free, very low viscosityaliphatic polyisocyanate Tolonate ™ HDT 90 an aliphatic polyisocyanate,based on HDI-trimer (isocyanurate), supplied at 90% solids Tolonate ™HDT 90 B an aliphatic polyisocyanate, based on HDI-trimer(isocyanurate), supplied at 90% solids Tolonate ™ IDT 70 B an aliphaticpolyisocyanate, based on HDI-trimer (isocyanurate), supplied at 70%solids Tolonate ™ IDT 70 S an aliphatic polyisocyanate, based onHDI-trimer (isocyanurate), supplied at 70% solids Tolonate ™ X FD 90 B ahigh functionality, fast drying aliphatic polyisocyanate based on HDI-trimer, supplied at 90% solids

Other isocyanates suitable for certain embodiments of the presentinvention are sold under the trade name Mondur® available from BayerMaterial Science. In certain embodiments, the isocyanates are selectedfrom the group consisting of the materials shown in Table 4:

TABLE 4 Trade Name Description MONDUR 445 TDI/MDI blend polyisocyanate;blend of toluene diisocyanate and polymeric diphenylmethanediisocyanate; NCO weight 44.5-45.2% MONDUR 448 modified polymericdiphenylmethane diisocyanate (pMDI) prepolymer; NCO weight 27.7%;viscosity 140 mPa · s @ 25° C.; equivalent weight 152; functionality 2.2MONDUR 489 modified polymeric diphenylmethane diisocyanate (pMDI); NCOweight 31.5%; viscosity 700 mPa · s @ 25° C.; equivalent weight 133;functionality 3.0 MONDUR 501 modified monomeric diphenylmethanediisocyanate (mMDI); isocyanate- terminated polyester prepolymer; NCOweight 19.0%; viscosity 1,100 mPa · s @ 25° C.; equivalent weight 221;functionality 2 MONDUR 541 polymeric diphenylmethane diisocyanate(pMDI); binder for composite wood products and as a raw material inadhesive formulations; NCO weight 31.5%; viscosity 200 mPa · s @ 25° C.MONDUR 582 polymeric diphenylmethane diisocyanate (pMDI); binder forcomposite wood products and as a raw material in adhesive formulations;NCO weight 31.0%; viscosity 200 mPa · s @ 25° C. MONDUR 541-Lightpolymeric diphenylmethane diisocyanate (pMDI); NCO weight 32.0%;viscosity 70 mPa · s @ 25° C.; equivalent weight 131; functionality 2.5MONDUR 841 modified polymeric MDI prepolymer; NCO, Wt 30.5%; Acidity, Wt0.02%; Amine Equivalent 132; Viscosity at 25° C., mPa · s 350; Specificgravity at 25° C. 1.24; Flash Point, PMCC, ° F. >200 MONDUR 1437modified diphenylmethane diisocyanate (mMDI); isocyanate-terminatedpolyether prepolymer; NCO weight 10.0%; viscosity 2,500 mPa · s @ 25°C.; equivalent weight 420; functionality 2 MONDUR 1453 modifieddiphenylmethane diisocyanate (mMDI); isocyanate-terminated polyetherprepolymer based on polypropylene ether glycol (PPG); NCO weight 16.5%;viscosity 600 mPa · s @ 25° C.; equivalent weight 254; functionality 2MONDUR 1515 modified polymeric diphenylmethane diisocyanate (pMDI)prepolymer; used in the production of rigid polyurethane foams,especially for the appliance industry; NCO weight 30.5%; viscosity 350mPa · s @ 25° C. MONDUR 1522 modified monomeric 4,4-diphenylmethanediisocyanate (mMDI); NCO weight 29.5%; viscosity 50 mPa · s @ 25° C.;equivalent weight 143; functionality 2.2 MONDUR MA-2300 modifiedmonomeric MDI, allophanate-modified 4,4

diphenylmethane diisocyanate (mMDI); NCO weight 23.0%; viscosity 450 mPa· s @ 25° C.; equivalent weight 183; functionality 2.0 MONDUR MA 2600modified monomeric MDI, allophanate-modified 4,4

diphenylmethane diisocyanate (mMDI); NCO weight 26.0%; viscosity 100 mPa· s @ 25° C.; equivalent weight 162; functionality 2.0 MONDUR MA 2601aromatic diisocyanate blend, allophanate-modified 4,4

diphenylmethane diisocyanate (MDI) blended with polymericdiphenylmethane diisocyanate (pMDI) containing 2,4

isomer; NCO weight 29.0%; viscosity 60 mPa · s @ 25° C.; equivalentweight 145; functionality 2.2 MONDUR MA 2603 MDI prepolymer;isocyanate-terminated (MDI) prepolymer blended with anallophanate-modified 4,4

diphenylmethane diisocyanate (MDI); NCO weight 16.0%; viscosity 1,050mPa · s @ 25° C.; equivalent weight 263; functionality 2.0 MONDURMA-2902 modified monomeric MDI, allophanate-modified 4,4

diphenylmethane diisocyanate (mMDI); NCO weight 29.0%; viscosity 40 mPa· s @25° C.; equivalent weight 145; functionality 2.0 MONDUR MA-2903modified monomeric MDI; isocyanate-terminated (MDI) prepolymer; NCOweight 19.0%; viscosity 400 mPa · s @ 25° C.; equivalent weight 221;functionality 2.0 MONDUR MA-2904 Allophanate-modified MDI polyetherprepolymer; NCO weight 12.0%; viscosity 1,800 mPa · s @ 25° C.;equivalent weight 350; functionality of 2.0 MONDUR MB high-purity gradedifunctional isocyanante, diphenylmethane 4,4

diiscocyanate; used in production of polyurethane elastomers, adhesives,coatings and intermediate polyurethane products; appearance colorlesssolid or liquid; specific gravity @ 50° C. ± 15.5 1.19; flash point 202°C. PMCC; viscosity (in molten form) 4.1 mPa · S; bult density 10 lb/gal(fused) or 9.93 lb/gal (molten); freezing temperature 39° C. MONDUR MLQmonomeric diphenylmethan diisocyanate; used in a foams, cast elastomers,coatings and andesives; appearance light yellow clear liquid, NCO 33.4%wt; 1.19 specific gravity at 25° C., 196° C. flash point, DIN 51758;11-15° C. freezing temperature MONDUR MQ high-purity-grade difunctionalisocyanate, diphenylmethane 4,4

diisocyanate (MDI); used in production of solid polyurethane elastomers,adhesives, coatings and in intermediate polyurethane products;appearance colorless solid or liquid; specific gravity 1.19 @ 50° C.;flash point 202° C. PMCC; viscosity 4.1 mPa · S; bulk density 10 lb./gal(fused) or 9.93 lb./gal (molten); freezing temperature 39° C. MONDUR MRpolymeric diphenylmethane diisocyanate (pMDI); NCO weight 31.5%;viscosity 200 mPa · s @ 25° C.; equivalent weight 133; functionality 2.8MONDUR MR polymeric diphenylmethane diisocyanate (pMDI); NCO weight31.5%; viscosity LIGHT 200 mPa · s @ 25° C.; equivalent weight 133;functionality 2.8 MONDUR MR-5 polymeric diphenylmethane diisocyanate(pMDI); NCO weight 32.5%; viscosity 50 mPa · s @ 25° C.; equivalentweight 129; functionality 2.4 MONDUR MRS 2,4

rich polymeric diphenylmethane diisocyanate (pMDI); NCO weight 31.5%;viscosity 200 mPa · s @ 25° C.; equivalent weight 133; functionality2.6MONDUR MRS 2 2,4

rich polymeric diphenylmethane diisocyanate (pMDI); NCO weight 33.0%;viscosity 25 mPa · s @ 25° C.; equivalent weight 127; functionality2.2MONDUR MRS-4 2,4

rich polymeric diphenylmethane diisocyanate (pMDI); NCO weight 32.5%;viscosity 40 mPa · s @ 25° C.; equivalent weight 129; functionality 2.4MONDUR MRS-5 2,4

rich polymeric diphenylmethane diisocyanate (pMDI); NCO weight 32.3%;viscosity 55 mPa · s @ 25° C.; equivalent weight 130; functionality 2.4MONDUR PC modified 4,4

diphenylmethane diisocyanate (mMDI); NCO weight 25.8%; viscosity 145 mPa· s @25° C.; equivalent weight 163; functionality 2.1 MONDUR PF modified4,4

diphenylmethane diisocyanate (mMDI) prepolymer; NCO weight 22.9%;viscosity 650 mPa · s @ 25° C.; equivalent weight 183; functionality 2MONDUR TD-65 monomeric toluene diisocyanate (TDI); 65/35 mixture of 2,4and 2.6 TDI; NCO weight 48%; viscosity 3 mPa · s @ 25° C.; equivalentweight 87.5; functionality 2 MONDUR TD-80 monomeric toluene diisocyanate(TDI); 80/20 mixture of the 2,4 and 2,6 isomer; GRADE A NCO weight 48%;viscosity 5 mPa · s @ 25° C.; equivalent weight 87.5; functionality 2MONDUR TD-80 monomeric toluene diisocyanate (TDI); 80/20 mixture of the2,4 and 2,6 isomer; GRADE A/GRADE B NCO weight 48%; viscosity 5 mPa · s@ 25° C.; equivalent weight 87.5; functionality 2

In certain embodiments, one or more of the above-described isocyanatecompositions is provided in a formulation typical of an A-side mixtureknown in the art of polyurethane foam manufacture. Such A side mixturesmay comprise prepolymers formed by the reaction of a molar excess of oneor more polyisocyanates with reactive molecules comprising reactivefunctional groups such as alcohols, amines, thiols, carboxylates and thelike. A-side mixtures may also comprise solvents, surfactants,stabilizers, and other additives known in the art.

III. B-Side Mixtures

As described above, in some embodiments, compositions of the presentinvention comprise so-called B-side mixtures comprising one or more ofthe aliphatic polycarbonate polyols described in Section I above.Additional aliphatic polycarbonate polyols suitable for the formulationof B-side mixtures of the present invention are disclosed inPCT/US2010/028362, published as WO/2010/028362.

In certain embodiments, the B-side mixture comprises the aliphaticpolycarbonate polyols in combination with one or more additional polyolsand/or one or more additives. In certain embodiments, the additives areselected from the group consisting of: solvents, water, catalysts,surfactants, blowing agents, colorants, UV stabilizers, flameretardants, antimicrobials, plasticizers, cell-openers, antistaticcompositions, compatibilizers, and the like. In certain embodiments, theB-side mixtures comprise additional reactive small molecules such asamines, alcohols, thiols or carboxylic acids that participate inbond-forming reactions with isocyanates.

Additional Polyols

In certain embodiments, the B-side mixtures of the present inventioncomprise aliphatic polycarbonate polyols as described above incombination with one or more additional polyols such as aretraditionally used in polyurethane foam compositions. In embodimentswhere additional polyols are present, they may comprise up to about 95weight percent of the total polyol content with the balance of thepolyol mixture made up of one or more aliphatic polycarbonate polyolsdescribed in Section I above and in the examples and specificembodiments herein.

In embodiments where B-side mixtures of the present invention compriseor derived from a mixture of one or more aliphatic polycarbonate polyolsand one or more additional polyols, the additional polyols are selectedfrom the group consisting of polyether polyols, polyester polyols,polystyrene polyols, polyether-carbonate polyols, polyether-estercarbonates, and mixtures of any two or more of these. In certainembodiments, B-side mixtures of the present invention comprise orderived from a mixture of one or more aliphatic polycarbonate polyols asdescribed herein and one or more other polyols selected from the groupconsisting of materials available commercially under the trade names:Voranol® (Dow), SpecFlex® (Dow), Tercarol® (Dow), Caradol® (Shell),Hyperliter®, Acclaim® (Bayer Material Science), Ultracel® (BayerMaterial Science), Desmophen® (Bayer Material Science), and Arcol®(Bayer Material Science).

In certain embodiments, B-side mixtures of the present inventioncomprise mixtures containing polyether polyols in combination with oneor more aliphatic polycarbonate polyols as described herein. In certainembodiments, such polyether polyols are characterized in that they havean Mn between about 500 and about 10,000 g/mol. In certain embodiments,such polyether polyols have an Mn between about 500 and about 5,000g/mol. In certain embodiments, the polyether polyols comprisepolyethylene glycol. In certain embodiments, the polyether polyolscomprise polypropylene glycol.

Polyether polyols that may be present include those which can beobtained by known methods, for example, polyether polyols can beproduced by anionic polymerization with alkali hydroxides such as sodiumhydroxide or potassium hydroxide or alkali alcoholates, such as sodiummethylate, sodium ethylate, potassium ethylate or potassium isopropylateas catalysts and with the addition of at least one initiator moleculecontaining 2 to 8, preferably 3 to 8, reactive hydrogens or by cationicpolymerization with Lewis acids such as antimony pentachloride, borontrifluoride etherate, etc., or bleaching earth as catalysts from one ormore alkylene oxides with 2 to 4 carbons in the alkylene radical. Anysuitable alkylene oxide may be used such as 1,3-propylene oxide, 1,2-and 2,3 butylene oxide, amylene oxides, styrene oxide, and preferablyethylene oxide and propylene oxide and mixtures of these oxides. Thepolyalkylene polyether polyols may be prepared from other startingmaterials such as tetrahydrofuran and alkylene oxide-tetrahydrofuranmixtures; epihalohydrins such as epichlorohydrin; as well as aralkyleneoxides such as styrene oxide. The polyalkylene polyether polyols mayhave either primary or secondary hydroxyl groups, preferably secondaryhydroxyl groups from the addition of propylene oxide onto an initiatorbecause these groups are slower to react. Included among the polyetherpolyols are polyoxyethylene glycol, polyoxypropylene glycol,polyoxybutylene glycol, polytetramethylene glycol, block copolymers, forexample, combinations of polyoxypropylene and polyoxyethylene glycols,poly-1,2-oxybutylene and polyoxyethylene glycols,poly-1,4-tetramefhylene and polyoxyethylene glycols, and copolymerglycols prepared from blends or sequential addition of two or morealkylene oxides. The polyalkylene polyether polyols may be prepared byany known process such as, for example, the process disclosed by Wurtzin Encyclopedia of Chemical Technology, Vol. 7, pp. 257-262, publishedby Interscience Publishers, Inc. (1951) or in U.S. Pat. No. 1,922,459.Polyethers include the alkylene oxide addition products of polyhydricalcohols such as ethylene glycol, propylene glycol, dipropylene glycol,trimethylene glycol, 1,2-butanediol, 1,5-pentanediol, 1,6hexanediol,1,7-heptanediol, hydroquinone, resorcinol glycerol, glycerine,1,1,1-trimethylol-propane, 1,1,1trimethylolethane, pentaerythritol,1,2,6-hexanetriol, a-methyl glucoside, sucrose, and sorbitol. Alsoincluded within the term “polyhydric alcohol” are compounds derived fromphenol such as 2,2-bis(4-hydroxyphenyl)-propane, commonly known asBisphenol A. Particularly preferred in the polyol composition is atleast one polyol which is initiated with a compound having at least twoprimary or secondary amine groups, a polyhydric alcohol having 4 or morehydroxyl groups, such as sucrose, or a mixture of initiators employing apolyhydric alcohol having at least 4 hydroxyl groups and compoundshaving at least two primary or secondary amine groups. Suitable organicamine initiators which may be condensed with alkylene oxides includearomatic amines-such as aniline, N-alkylphenylene-diamines, 2,4

,2,2

, and 4,4

methylenedianiline, 2,6- or 2,4-toluenediamine, vicinal toluenediamines,o-chloroaniline, p-aminoaniline, 1,5-diaminonaphthalene, methylenedianiline, the various condensation products of aniline andformaldehyde, and the isomeric diaminotoluenes; and aliphatic aminessuch as mono-, di-, and trialkanolamines, ethylene diamine, propylenediamine, diethylenetriamine, methylamine, triisopropanolamine,1,3-diaminopropane, 1,3-diaminobutane, and 1,4-diaminobutane. Preferableamines include monoethanolamine, vicinal toluenediamines,ethylenediamines, and propylenediamine. Yet another class of aromaticpolyether polyols contemplated for use in this invention are theMannich-based polyol an alkylene oxide adduct ofphenol/formaldehyde/alkanolamine resin, frequently called a “Mannich”polyol such as disclosed in U.S. Pat. Nos. 4,883,826; 4,939,182; and5,120, 815.

In certain embodiments where additional polyols are present, theycomprise from about 5 weight percent to about 95 weight percent of thetotal polyol content with the balance of the polyol mixture made up ofone or more aliphatic polycarbonate polyols described in Section I aboveand in the examples and specific embodiments herein. In certainembodiments, up to about 75 weight percent of the total polyol contentof the B-side mixture is aliphatic polycarbonate polyol. In certainembodiments, up to about 50 weight percent of the total polyol contentof the B-side mixture is aliphatic polycarbonate polyol. In certainembodiments, up to about 40 weight percent, up to about 30 weightpercent, up to about 25 weight percent, up to about 20 weight percent,up to about 15 weight percent, or up to about 10 weight percent of thetotal polyol content of the B-side mixture is aliphatic polycarbonatepolyol. In certain embodiments, at least about 5 weight percent of thetotal polyol content of the B-side mixture is aliphatic polycarbonatepolyol. In certain embodiments, at least about 10 weight percent of thetotal polyol content of the B-side mixture is aliphatic polycarbonatepolyol. In certain embodiments, at least about 15 weight percent, atleast about 20 weight percent, at least about 25 weight percent, atleast about 40 weight percent, or at least about 50 weight percent, ofthe total polyol content of the B-side mixture is aliphaticpolycarbonate polyol.

Catalysts

In certain embodiments, B-side mixtures contain one or more catalystsfor the reaction of the polyol (and water, if present) with thepolyisocyanate. Any suitable urethane catalyst may be used, includingtertiary amine compounds and organometallic compounds. Exemplarytertiary amine compounds include triethylenediamine, N-methylmorpholine,N,N-dimethylcyclohexyl amine, pentamethyldiethylenetriamine,tetramethylethylenediamine, 1-methyl-4-dimethylaminoethylpiperazine,3-methoxy-N-dimethylpropylamine, N-ethylmorpholine, diethylethanolamine,N-cocomorpholine, N,N-dimethyl-N

N

-dimethyl isopropylpropylenediamine,N,N-diethyl-3-diethylaminopropylamine dimethylbenzylamine,1,8-Diazabicycloundec-7-ene (DBU), 1,4-diazabicyclo[2.2.2]octane (DABCO)triazabicyclodecene (TBD), and N-methyltriazabicyclodecene. (MTBD)Exemplary organometallic catalysts include organomercury, organolead,organoferric and organotin catalysts, with organotin catalysts beingpreferred among these. Suitable tin catalysts include stannous chloride,tin salts of carboxylic acids such as dibutyltin dilaurate, as well asother organometallic compounds such as are disclosed in U.S. Pat. No.2,846,408 and elsewhere. A catalyst for the trimerization ofpolyisocyanates, resulting in a polyisocyanurate, such as an alkalimetal alkoxide may also optionally be employed herein. Such catalystsare used in an amount which measurably increases the rate ofpolyurethane or polyisocyanurate formation.

In certain embodiments, where B-side mixtures of the present inventioncomprise catalysts, the catalysts comprise tin based materials. Incertain embodiments, tin catalysts included in the B-side mixtures areselected from the group consisting of: di-butyl tin dilaurate,dibutylbis(laurylthio)stannate, dibutyltinbis(isooctylmercapto acetate)and dibutyltinbis(isooctylmaleate), tin octanoate and mixtures of anytwo or more of these.

In certain embodiments, catalysts included in the B-side mixturescomprise tertiary amines. In certain embodiments, catalysts included inthe B-side mixtures are selected from the group consisting of: DABCO,pentametyldipropylenetriamine, bis(dimethylamino ethyl ether),pentamethyldiethylenetriamine, DBU phenol salt, dimethylcyclohexylamine,2,4,6-tris(N,N-dimethylaminomethyl)phenol (DMT-30),1,3,5-tris(3-dimethylaminopropyl)hexahydro-s-triazine, ammonium saltsand combinations or formulations of any of these.

Typical amounts of catalyst are 0.001 to 10 parts of catalyst per 100parts by weight of total polyol in the B-side mixture. In certainembodiments, catalyst levels in the formulation, when used, rangebetween about 0.001 pph (weight parts per hundred) and about 3 pph basedon the amount of polyol present in the B-side mixture. In certainembodiments, catalyst levels range between about 0.05 pph and about 1pph, or between about 0.1 pph and about 0.5 pph.

Blowing Agents

In certain embodiments, B-side mixtures of the present invention containblowing agents. Blowing agents may be chemical blowing agents (typicallymolecules that react with A-side components to liberate CO₂ or othervolatile compounds) or they may be physical blowing agents (typicallymolecules with a low boiling point that vaporize during the foamformation. Many blowing agents are known in the art and may be appliedto B-side compositions of the present invention according toconventional methodology. The choice of blowing agent and the amountsadded can be a matter of routine experimentation.

In certain embodiments, the blowing agent comprises a chemical blowingagent. In certain embodiments, water is present as a blowing agent.Water functions as a blowing agent by reacting with a portion of theisocyanate in the A-side mixture to produce carbon dioxide gas.Similarly, formic acid can be included as a blowing agent. Formic acidfunctions as a blowing agent by reacting with a portion of theisocyanate to produce carbon dioxide and carbon monoxide gas.

In certain embodiments, water is present in an amount of from 0.5 to 20parts per 100 parts by weight of the polyol in the B-side composition.In certain embodiments, water is present from about 1 to 10 parts, fromabout 2 to 8 parts, or from about 4 to 6 parts per 100 parts by weightof polyol in the B-side composition. In certain embodiments, it isadvantageous not to exceed 2 parts of water, not-to exceed 1.5 parts ofwater, or not to exceed 0.75 parts of water. In certain embodiments, itis advantageous to have water absent.

In certain embodiments, formic acid is present in an amount of from 0.5to 20 parts per 100 parts by weight of the polyol in the B-sidecomposition. In certain embodiments, formic acid is present from about 1to 10 parts, from about 2 to 8 parts, or from about 4 to 6 parts per 100parts by weight of polyol in the B-side composition.

In certain embodiments physical blowing agents can be used. Suitablephysical blowing agents include hydrocarbons, fluorine-containingorganic molecules hydrocarbons, chlorocarbons, acetone, methyl formateand carbon dioxide. In some embodiments, fluorine-containing organicmolecules comprise perfluorinated compounds, chlorofluorocarbons,hydrochlorofluorocarbons, and hydrofluorocarbons. Suitablehydrofluoroalkanes are C₁₋₄ compounds including difiuoromethane (R-32),1,1,1,2-tetrafluoroethane (R-134a), 1,1-difluoroethane (R-152a),difiuorochloroethane (R-142b), trifiuoromethane (R-23),heptafluoropropane (R-227a), hexafluoropropane (R136),1,1,1-trifluoroefhane (R-133), fluoroethane (R-161),1,1,1,2,2-pentafluoropropane (R-245fa), pentafluoropropylene (R2125a),1,1,1,3-tetrafiuoropropane, tetrafhioropropylene (R-2134a),1,1,2,3,3-pentafluoropropane and 1,1,1,3,3-pentafiuoro-n-butane.

In certain embodiments, when a hydrofluorocarbon blowing agent ispresent in the B-side mixture, it is selected from the group consistingof: tetrafluoroethane (R-134a), pentafluoropropane (R-245fa) andpentafluorobutane (R-365).

Suitable hydrocarbons for use as blowing agent include nonhalogenatedhydrocarbons such as butane, isobutane, 2,3-dimethylbutane, n- andi-pentane isomers, hexane isomers, heptane isomers and cycloalkanesincluding cyclopentane, cyclohexane and cycloheptane. Preferredhydrocarbons for use as blowing agents include cyclopentane and notablyn-pentane an iso-pentane. In a certain embodiments the B-sidecomposition comprises a physical blowing agent selected from the groupconsisting of tetrafluoroethane (R-134a), pentafluoropropane (R-245fa),pentafluorobutane (R-365), cyclopentane, n-pentane and iso-pentane.

In certain embodiments where a physical blowing agent is present, it isused in an amount of from about 1 to about 20 parts per 100 parts byweight of the polyol in the B-side composition. In certain embodiments,the physical blowing agent is present from 2 to 15 parts, or from 4 to10 parts per 100 parts by weight of the polyol in the B-sidecomposition.

Reactive Small Molecules

In certain embodiments, B-side mixtures of the present invention includeone or more small molecules reactive toward isocyanates. In certainembodiments, reactive small molecules included in the inventive B-sidemixtures comprise organic molecules having one or more functional groupsselected from the group consisting of alcohols, amines, carboxylicacids, thiols, and combinations of any two or more of these. In someembodiments, a non-polymeric small molecule has a molecular weight lessthan 1,000 g/mol, or less than 1,500 g/mol.

In certain embodiments, B-side mixtures of the present invention includeone or more alcohols. In certain embodiments, the B-side mixturesinclude polyhydric alcohols.

In certain embodiments, reactive small molecules included in theinventive B-side mixtures comprise dihydric alcohols. In certainembodiments, the dihydric alcohol comprises a C₂₋₄₀ diol. In certainembodiments, the dihydric alcohol is selected from the group consistingof: 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol,1,3-butanediol, 1,4-butanediol, 1,5-pentanediol,2,2-dimethylpropane-1,3-diol, 2-butyl-2-ethylpropane-1,3-diol,2-methyl-2,4-pentane diol, 2-ethyl-1,3-hexane diol, 2-methyl-1,3-propanediol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol,1,12-dodecanediol, 2,2,4,4-tetramethylcyclobutane-1,3-diol,1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol,1,4-cyclohexanediol, 1,2-cyclohexanedimethanol,1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol,1,4-cyclohexanediethanol, isosorbide, glycerol monoesters, glycerolmonoethers, trimethylolpropane monoesters, trimethylolpropanemonoethers, pentaerythritol diesters, pentaerythritol diethers, andalkoxylated derivatives of any of these.

In certain embodiments, a reactive small molecule included in theinventive B-side mixtures comprises a dihydric alcohol selected from thegroup consisting of: diethylene glycol, triethylene glycol,tetraethylene glycol, higher poly(ethylene glycol), such as those havingnumber average molecular weights of from 220 to about 2000 g/mol,dipropylene glycol, tripropylene glycol, and higher poly(propyleneglycols) such as those having number average molecular weights of from234 to about 2000 g/mol.

In certain embodiments, a reactive small molecule included in theinventive B-side mixtures comprises an alkoxylated derivative of acompound selected from the group consisting of: a diacid, a diol, or ahydroxy acid. In certain embodiments, the alkoxylated derivativescomprise ethoxylated or propoxylated compounds.

In certain embodiments, a reactive small molecule included in theinventive B-side mixtures comprises a polymeric diol. In certainembodiments, a polymeric diol is selected from the group consisting ofpolyethers, polyesters, hydroxy-terminated polyolefins,polyether-copolyesters, polyether polycarbonates,polycarbonate-copolyesters, and alkoxylated analogs of any of these. Incertain embodiments, the polymeric diol has an average molecular weightless than about 2000 g/mol.

In some embodiments, a reactive small molecule included in the inventiveB-side mixtures comprises a triol or higher polyhydric alcohol. Incertain embodiments, a reactive small molecule is selected from thegroup consisting of: glycerol, 1,2,4-butanetriol,2-(hydroxymethyl)-1,3-propanediol; hexane triols, trimethylol propane,trimethylol ethane, trimethylolhexane, 1,4-cyclohexanetrimethanol,pentaerythritol mono esters, pentaerythritol mono ethers, andalkoxylated analogs of any of these. In certain embodiments, alkoxylatedderivatives comprise ethoxylated or propoxylated compounds.

In some embodiments, a reactive small molecule comprises a polyhydricalcohol with four to six hydroxy groups. In certain embodiments, acoreactant comprises dipentaerithrotol or an alkoxylated analog thereof.In certain embodiments, coreactant comprises sorbitol or an alkoxylatedanalog thereof.

In certain embodiments, a reactive small molecule comprises ahydroxy-carboxylic acid having the general formula (HO)_(x)Q(COOH)_(y),wherein Q is a straight or branched hydrocarbon radical containing 1 to12 carbon atoms, and x and y are each integers from 1 to 3. In certainembodiments, a coreactant comprises a diol carboxylic acid. In certainembodiments, a coreactant comprises a bis(hydroxylalkyl) alkanoic acid.In certain embodiments, a coreactant comprises a bis(hydroxylmethyl)alkanoic acid. In certain embodiments the diol carboxylic acid isselected from the group consisting of 2,2 bis-(hydroxymethyl)-propanoicacid (dimethylolpropionic acid, DMPA) 2,2-bis(hydroxymethyl) butanoicacid (dimethylolbutanoic acid; DMBA), dihydroxysuccinic acid (tartaricacid), and 4,4′-bis(hydroxyphenyl) valeric acid. In certain embodiments,a coreactant comprises an N,N-bis(2-hydroxyalkyl)carboxylic acid.

In certain embodiments, a reactive small molecule comprises a polyhydricalcohol comprising one or more amino groups. In certain embodiments, areactive small molecule comprises an amino diol. In certain embodiments,a reactive small molecule comprises a diol containing a tertiary aminogroup. In certain embodiments, an amino diol is selected from the groupconsisting of: diethanolamine (DEA), N-methyldiethanolamine (MDEA),N-ethyl di ethanol amine (EDEA), N-butyldiethanolamine (BDEA),N,N-bis(hydroxyethyl)-α-amino pyridine, dipropanolamine,diisopropanolamine (DIPA), N-methyldiisopropanolamine,Diisopropanol-p-toluidine, N,N-Bis(hydroxyethyl)-3-chloroaniline,3-diethylaminopropane-1,2-diol, 3-dimethylaminopropane-1,2-diol andN-hydroxyethylpiperidine. In certain embodiments, a coreactant comprisesa diol containing a quaternary amino group. In certain embodiments, acoreactant comprising a quaternary amino group is an acid salt orquaternized derivative of any of the amino alcohols described above.

In certain embodiments, a reactive small molecule is selected from thegroup consisting of: inorganic or organic polyamines having an averageof about 2 or more primary and/or secondary amine groups, polyalcohols,ureas, and combinations of any two or more of these. In certainembodiments, a reactive small molecule is selected from the groupconsisting of: diethylene triamine (DETA), ethylene diamine (EDA),meta-xylylenediamine (MXDA), aminoethyl ethanolamine (AEEA), 2-methylpentane diamine, and the like, and mixtures thereof. Also suitable forpractice in the present invention are propylene diamine, butylenediamine, hexamethylene diamine, cyclohexylene diamine, phenylenediamine, tolyl ene diamine, 3,3-di chlorobenzidene,4,4′-methylene-bis-(2-chloroaniline), 3,3-dichloro-4,4-diaminodiphenylmethane, and sulfonated primary and/or secondary amines. Incertain embodiments, reactive small molecule is selected from the groupconsisting of: hydrazine, substituted hydrazines, hydrazine reactionproducts, and the like, and mixtures thereof. In certain embodiments, areactive small molecule is a polyalcohol including those having from 2to 12 carbon atoms, preferably from 2 to 8 carbon atoms, such asethylene glycol, diethylene glycol, neopentyl glycol, butanediols,hexanediol, and the like, and mixtures thereof. Suitable ureas includeurea and its derivatives, and the like, and mixtures thereof.

In certain embodiments, reactive small molecules containing at least onebasic nitrogen atom are selected from the group consisting of: mono-,bis- or polyalkoxylated aliphatic, cycloaliphatic, aromatic orheterocyclic primary amines, N-methyl diethanolamine, N-ethyldiethanolamine, N-propyl diethanolamine, N-isopropyl diethanolamine,N-butyl diethanolamine, N-isobutyl diethanolamine, N-oleyldiethanolamine, N-stearyl diethanolamine, ethoxylated coconut oil fattyamine, N-allyl diethanolamine, N-methyl diisopropanolamine, N-ethyldiisopropanolamine, N-propyl diisopropanolamine, N-butyldiisopropanolamine, cyclohexyl diisopropanolamine, N,N-diethoxylaniline,N,N-diethoxyl toluidine, N,N-diethoxyl-1-aminopyridine, N,N′-diethoxylpiperazine, dimethyl-bis-ethoxyl hydrazine,N,N′-bis-(2-hydroxyethyl)-N,N′-diethylhexahydrop-phenylenediamine,N-12-hydroxyethyl piperazine, polyalkoxylated amines, propoxylatedmethyl diethanolamine, N-methyl-N,N-bis-3-aminopropylamine,N-(3-aminopropyl)-N,N′-dimethyl ethylenediamine,N-(3-aminopropyl)-N-methyl ethanolamine,N,N′-bis-(3-aminopropyl)-N,N′-dimethyl ethylenediamine,N,N′-bis-(3-aminopropyl)-piperazine, N-(2-aminoethyl)-piperazine, N,N′-bisoxyethyl propylenediamine, 2,6-diaminopyridine,diethanolaminoacetamide, diethanolamidopropionamide,N,N-bisoxyethylphenyl thiosemicarbazide, N,N-bis-oxyethylmethylsemicarbazide, p,p′-bis-aminomethyl dibenzyl methylamine,2,6-diaminopyridine, 2-dimethylaminomethyl-2-methylpropanel, 3-diol. Incertain embodiments, chain-extending agents are compounds that containtwo amino groups. In certain embodiments, chain-extending agents areselected from the group consisting of: ethylene diamine,1,6-hexamethylene diamine, and 1,5-diamino-1-methyl-pentane.

Additives

In addition to the above components, B-side mixtures of the presentinvention may optionally contain various additives as are known in theart of polyurethane foam technology. Such additives may include, but arenot limited to compatibilizers, colorants, surfactants, flameretardants, antistatic compounds, antimicrobials, UV stabilizers,plasticizers, and cell openers.

—Colorants

In certain embodiments, B-side mixtures of the present inventioncomprise one or more suitable colorants. Many foam products are colorcoded during manufacture to identify product grade, to concealyellowing, or to make a consumer product. The historical method ofcoloring foam was to blend in traditional pigments or dyes. Typicalinorganic coloring agents included titanium dioxide, iron oxides andchromium oxide. Organic pigments originated from the azo/diazo dyes,phthalocyanines and dioxazines, as well as carbon black. Typicalproblems encountered with these colorants included high viscosity,abrasive tendencies, foam instability, foam scorch, migrating color anda limited range of available colors. Recent advances in the developmentof polyol-bound colorants are described in:

-   Miley, J. W.; Moore, P. D. “Reactive Polymeric Colorants For    Polyurethane”, Proceedings Of The SPI-26th Annual Technical    Conference; Technomic: Lancaster, Pa., 1981; 83-86.-   Moore, P. D.; Miley, J. W.; Bates, S. H.; “New Uses For Highly    Miscible Liquid Polymeric Colorants In The Manufacture of Colored    Urethane Systems”; Proceedings of the SPI-27th Annual    Technical/Marketing Conference; Technomic: Lancaster, Pa., 1982;    255-261.-   Bates, S. H.; Miley, J. W. “Polyol-Bound Colorants Solve    Polyurethane Color Problems”; Proceedings Of The SPI-30th Annual    Technical/Marketing Conference; Technomic: Lancaster, Pa., 1986;    160-165-   Vielee, R. C.; Haney, T. V. “Polyurethanes”; In Coloring of    Plastics; Webber, T. G., Ed., Wiley-Interscience: New York, 1979,    191-204.

—UV Stabilizers

In certain embodiments, B-side mixtures of the present inventioncomprise one or more suitable UV stabilizers. Polyurethanes based onaromatic isocyanates will typically turn dark shades of yellow uponaging with exposure to light. A review of polyurethane weatheringphenomena is presented in: Davis, A.; Sims, D. Weathering Of Polymers;Applied Science: London, 1983, 222-237. The yellowing is not a problemfor most foam applications. Light protection agents, such ashydroxybenzotriazoles, zinc dibutyl thiocarbamate, 2,6-ditertiarybutylcatechol, hydroxybenzophenones, hindered amines and phosphites havebeen used to improve the light stability of polyurethanes. Colorpigments have also been used successfully.

—Flame Retardants

In certain embodiments, B-side mixtures of the present inventioncomprise one or more suitable flame retardants. Low-density, open-celledflexible polyurethane foams have a large surface area and highpermeability to air and thus will burn given the application ofsufficient ignition source and oxygen. Flame retardants are often addedto reduce this flammability. The choice of flame retardant for anyspecific foam often depends upon the intended service application ofthat foam and the attendant flammability testing scenario governing thatapplication. Aspects of flammability that may be influenced by additivesinclude the initial ignitability, burning rate and smoke evolution.

The most widely used flame retardants are the chlorinated phosphateesters, chlorinated paraffins and melamine powders. These and many othercompositions are available from specialty chemical suppliers. A reviewof this subject has been given: Kuryla, W. C.; Papa, A. J. FlameRetardancy of Polymeric Materials, Vol. 3; Marcel Dekker: New York,1975, 1-133.

—Bacteriostats

Under certain conditions of warmth and high humidity, polyurethane foamsare susceptible to attack by microorganisms. When this is a concern,additives against bacteria, yeast or fungi are added to the foam duringmanufacture. In certain embodiments, B-side mixtures of the presentinvention comprise one or more suitable bacteriostats.

—Plasticizers

In certain embodiments, B-side mixtures of the present inventioncomprise one or more suitable plasticizers. Nonreactive liquids havebeen used to soften a foam or to reduce viscosity for improvedprocessing. The softening effect can be compensated for by using apolyol of lower equivalent weight, so that a higher cross-linked polymerstructure is obtained. These materials increase foam density and oftenadversely affect physical properties.

—Cell-Openers

In certain embodiments, B-side mixtures of the present inventioncomprise one or more suitable cell openers. In some polyurethane foamsit is necessary to add cell-openers to obtain foam that does not shrinkupon cooling. Known additives for inducing cell-opening includesilicone-based antifoamers, waxes, finely divided solids, liquidperfluocarbons, paraffin oils, long-chain fatty acids and certainpolyether polyols made using high concentrations of ethylene oxide.

—Antistatic Agents

In certain embodiments, B-side mixtures of the present inventioncomprise one or more suitable antistatic compounds. Some flexible foamsare used in packaging, clothing and other applications where it isdesired to minimize the electrical resistance of the foam so thatbuildup of static electrical charges is minimized. This hastraditionally been accomplished through the addition of ionizable metalsalts, carboxylic acid salts, phosphate esters and mixtures thereof.These agents function either by being inherently conductive or byabsorbing moisture from the air. The desired net result is orders ofmagnitude reduction in foam surface resistivity.

—Compatibilizers

In certain embodiments, B-side mixtures of the present inventioncomprise one or more suitable compatibilizers. Compatibilizers aremolecules that allow two or more nonmiscible ingredients to cometogether and give a homogeneous liquid phase. Many such molecules areknown to the polyurethane industry, these include: amides, amines,hydrocarbon oils, phthalates, polybutyleneglycols, and ureas.

Compositions of Specific B-Side Mixtures

In certain embodiments, the present invention encompasses B-sidemixtures suitable for the formation of polyurethane foams wherein theB-side mixtures comprise:

-   -   100 parts by weight of a polyol component, wherein the polyol        component comprises from about 5 weight percent to 100 weight        percent of one or more of the aliphatic polycarbonate polyols        described above and in the specific embodiments and examples        herein;    -   0.01 to 20 parts by weight of one or more blowing agents as        described above and in the specific embodiments and examples        herein;    -   0 to 1 parts by weight of one or more catalysts as described        above and in the specific embodiments and examples herein;    -   0 to 20 parts by weight of one or more reactive small molecules,        wherein the reactive small molecules are substantially as        described above and in the specific embodiments and examples        herein; and    -   0 to 10 parts by weight of one or more additives, wherein the        additives are selected from the group consisting of:        compatibilizers, colorants, surfactants, flame retardants,        antistatic compounds, antimicrobials, UV stabilizers,        plasticizers, and cell openers substantially as described above        and in the specific embodiments and examples herein.;

In certain embodiments, the present invention encompasses a B-sidemixture denoted PEC-1 wherein the polyol component comprises 5 to 100weight percent poly(ethylene carbonate) polyol, said poly(ethylenecarbonate) characterized in that it has an Mn less than about 7000 g/moland greater than 99% hydroxyl end groups.

In certain embodiments, B-side mixtures PEC-B1 are characterized in thatthe poly(ethylene carbonate) polyol has an Mn less than about 5,000g/mol, less than about 4,000 g/mol, less than about 3,000 g/mol, lessthan about 2,500 g/mol, or less than about 2,000 g/mol. In certainembodiments, the poly(ethylene carbonate) polyol has an Mn of betweenabout 500 g/mol and about 3,000 g/mol. In certain embodiments, thepoly(ethylene carbonate) polyol has an Mn of between about 500 g/mol andabout 2,500 g/mol. In certain embodiments, the poly(ethylene carbonate)polyol has an Mn of between about 500 g/mol and about 2,000 g/mol.

In certain embodiments, B-side mixtures PEC-B1 are characterized in thatthe poly(ethylene carbonate) polyol has greater than 99%, greater than99.5%, greater than 99.7%, greater than 99.8% or greater than about99.9% —OH end groups.

In certain embodiments, B-side mixtures PEC-B1 are characterized in thatthe poly(ethylene carbonate) polyol has a polydispersity index (PDI)less than about 1.8. In certain embodiments, the poly(ethylenecarbonate) polyol has a PDI less than about 1.5, less than about 1.4,less than about 1.3, or less than about 1.2. In certain embodiments, thepoly(ethylene carbonate) polyol is characterized in that it has a PDIbetween about 1.05 and about 1.2.

In certain embodiments, B-side mixtures PEC-B1 are characterized in thatthe poly(ethylene carbonate) polyol contains, on average, greater thanabout 80% carbonate linkages. In certain embodiments, the poly(ethylenecarbonate) polyol contains, on average, greater than about 85%, greaterthan about 90%, greater than about 92%, greater than about 95%, greaterthan about 97%, greater than about 98%, or greater than about 99%carbonate linkages. In certain embodiments, the poly(ethylene carbonate)polyol contains, on average, less than about 15% ether linkages. Incertain embodiments, the % carbonate linkage and/or percent etherlinkage characteristics are defined as being exclusive of any embeddedchain transfer agent that may be embedded in the polycarbonate polyolchain.

In certain embodiments, B-side mixtures PEC-B1 are characterized in thatthe included poly(ethylene carbonate) polyol has a viscosity below100,000 centipoise at 20 degrees celcius. In certain embodiments,poly(ethylene carbonate) polyol has a viscosity below 15,000 centipoiseat 20 degrees celcius. In certain embodiments, the poly(ethylenecarbonate) polyol has a viscosity below 10,000 centipoise, below 6,000centipoise, or below 4,000 centipoise, all at 20 degrees celcius. Incertain embodiments, the poly(ethylene carbonate) poly has a viscositybelow 2,000 centipoise at 20 degrees celcius.

In certain embodiments, B-side mixtures PEC-B1 are further characterizedin that the poly(ethylene carbonate) polyol has a formula P2c:

-   -   wherein each —Y is —H, and each of        , and n is as defined above and described in classes and        subclasses herein.

In certain embodiments, B-side mixtures PEC-B1 are characterized in thatthe poly(ethylene carbonate) polyol has a formula Q1:

-   -   wherein t is an integer from 1 to 11 and n is as defined above        and in the specific embodiments and examples herein.

In certain embodiments, where B-side compositions comprise polyols offormula Q1, t is an integer between 1 and 5. In certain embodiments, tis 1. In certain embodiments, t is 2. In certain embodiments, t is 3. Incertain embodiments, t is 4. In certain embodiments, t is 5.

In certain embodiments, B-side mixtures PEC-B1 are characterized in thatthe poly(ethylene carbonate) polyol has a formula Q4:

-   -   wherein R^(t) is independently at each occurrence —H, or —CH₃,        and each of n and t is as defined above and described in the        specific examples and embodiments herein.

In certain embodiments, where B-side compositions comprise polyols offormula Q4, t is an integer between 1 and 3. In certain embodiments, tis 1. In certain embodiments, t is 2. In certain embodiments, t is 3.

In certain embodiments, the present invention encompasses a B-sidemixture denoted PPC-1 containing 100 parts by weight of a polyolcomponent, wherein the polyol component comprises 5 to 100 weightpercent poly(propylene carbonate) polyol, said poly(propylene carbonate)characterized in that it has an Mn less than about 7000 g/mol andgreater than 99% hydroxyl end groups.

In certain embodiments, B-side mixtures PPC-B1 are characterized in thatthe poly(propylene carbonate) polyol has an Mn less than about 5,000g/mol, less than about 4,000 g/mol, less than about 3,000 g/mol, lessthan about 2,500 g/mol, or less than about 2,000 g/mol. In certainembodiments, the poly(propylene carbonate) polyol has an Mn of betweenabout 500 g/mol and about 3,000 g/mol. In certain embodiments, thepoly(propylene carbonate) polyol has an Mn of between about 500 g/moland about 2,500 g/mol. In certain embodiments, the poly(propylenecarbonate) polyol has an Mn of between about 500 g/mol and about 2,000g/mol.

In certain embodiments, B-side mixtures PPC-B1 are characterized in thatthe poly(propylene carbonate) polyol has greater than 99%, greater than99.5%, greater than 99.7%, greater than 99.8% or greater than about99.9% —OH end groups.

In certain embodiments, B-side mixtures PPC-B1 are further characterizedin that the poly(propylene carbonate) polyol has a polydispersity index(PDI) less than about 1.8. In certain embodiments, the poly(propylenecarbonate) polyol has a PDI less than about 1.5, less than about 1.4,less than about 1.3, or less than about 1.2. In certain embodiments, thepoly(propylene carbonate) polyol is characterized in that it has a PDIbetween about 1.05 and about 1.2.

In certain embodiments, B-side mixtures PPC-B1 are further characterizedin that the poly(propylene carbonate) polyol contains, on average,greater than about 90% carbonate linkages. In certain embodiments, thepoly(ethylene carbonate) polyol contains, on average, greater than about95%, greater than about 97%, greater than about 98%, greater than about99%, greater than about 99.5%, or greater than about 99.9%, carbonatelinkages. In certain embodiments, the poly(propylene carbonate) polyolcontains no detectable ether linkages. In certain embodiments, the %carbonate linkage and/or percent ether linkage characteristics aredefined as being exclusive of any embedded chain transfer agent that maybe embedded in the polycarbonate polyol chain.

In certain embodiments, B-side mixtures PPC-B1 are further characterizedin that the included poly(propylene carbonate) polyol has a viscositybelow about 100,000 centipoise at 20 degrees celcius. In certainembodiments, the poly(ethylene carbonate) polyol has a viscosity below30,000 centipoise, below 15,000 centipoise, or below 12,000 centipoise,all at 20 degrees celcius. In certain embodiments, the poly(ethylenecarbonate) poly has a viscosity below 10,000 centipoise, 8,000centipoise, or 6,000 centipoise at 20 degrees celcius.

In certain embodiments, B-side mixtures PPC-B1 are further characterizedin that the poly(propylene carbonate) polyol has a formula P2a:

-   -   wherein each —Y is —H, and each of        and n is as defined above and described in classes and        subclasses herein.

In certain embodiments, B-side mixtures PPC-B1 are characterized in thatthe poly(ethylene carbonate) polyol has a formula Q2:

-   -   wherein each of t and n is as defined above and in the specific        embodiments and examples herein.

In certain embodiments, where B-side compositions comprise polyols offormula Q2, t is an integer between 1 and 5. In certain embodiments, tis 1. In certain embodiments, t is 2. In certain embodiments, t is 3. Incertain embodiments, t is 4. In certain embodiments, t is 5.

In certain embodiments, B-side mixtures PPC-B1 are characterized in thatthe poly(ethylene carbonate) polyol has a formula Q5:

-   -   wherein R^(t) is independently at each occurrence —H, or —CH₃,        and each of n and t is as defined above and described in the        specific examples and embodiments herein.

In certain embodiments, where B-side compositions comprise polyols offormula Q5, t is an integer between 1 and 3. In certain embodiments, tis 1. In certain embodiments, t is 2. In certain embodiments, t is 3.

In certain embodiments B-side mixtures PEC-B1 and PPC-B1 arecharacterized in that polyol component of the mixtures contain fromabout 5% to 100% of the described aliphatic polycarbonate polyol, withthe balance (if any) comprising one or more polyols typically used forpolyurethane foam formulation.

In certain embodiments where B-side mixtures PEC-B1 and PPC-B1 containless than 100% aliphatic polycarbonate polyol, the balance comprises apolyol selected from the group consisting of polyether polyols,polyester polyols, and combinations of these. In certain embodiments,the balance comprises a polyether polyol. In certain embodiments, thebalance comprises a polyester polyol.

IV. Foam Compositions

In another aspect, the present invention encompasses foams derived fromone or more of aliphatic polycarbonate polyol compositions describedabove and in the specific embodiments and examples disclosed herein. Incertain embodiments, the foam compositions comprise the reaction productof one or more polyisocyanates and a B-side mixture containing one ormore of the aliphatic polycarbonate polyol compositions defined above.

A. Flexible Foam Compositions

In one aspect, the present invention encompasses flexible foamcompositions. In certain embodiments, such flexible foam compositionsare derived from a B-side mixture containing one or more of thealiphatic polycarbonate polyol compositions as defined above and in theembodiments and examples herein.

In certain embodiments the flexible foam compositions comprise thereaction product of an A-side composition comprising polyfunctionalisocyanates with a B-side mixture of type PEC-B1, described above.

In certain embodiments the flexible foam compositions comprise thereaction product of an A-side composition comprising polyfunctionalisocyanates with a B-side mixture of type PPC-B1, described above.

Preferred B-side formulations for flexible foams have viscosities below100,000 centipoise, preferably below 6,000 centipoise at 20 degreescelcius. Preferred B-side polyols have OH numbers between 28 and 112.Preferred B-side polyols have acid numbers below 1. Preferred B-sidepolyols have functionalities between 1.9 and 3.0. Preferred A-sideformulations have isocyanate functionalities below 2.7.

Preferred finished flexible foams have Indentation Force Deflectionvalues targeted for specific end markets. The preferred force in poundsrequired to indent a 50 square inch round indentor to 25% on a 15″ by15″ by 4″ foam sample are: 6-12 pounds for bed pillows and thick backpillows; 12-18 pounds for back pillows, upholstery padding, and wraps;18-24 pounds for thin back pillows, tufting matrix, very thick seatcushions, and wraps. In some embodiments, finished foams havecompression set values below 20%, and more preferred below 15%, withmost preferred below 10%. Typical densities for finished flexible moldedfoams are between 2 and 3 pounds per cubic foot, and typical densitiesfor finished flexible slabstock foams between 1 and 4 pounds per cubicfoot, with most applications between 1 and 2 pounds per cubic foot.

B. Microcellular Foam Compositions

In one aspect, the present invention encompasses microcellular foamcompositions. In certain embodiments, such microcellular foamcompositions are derived from a B-side mixture containing one or more ofthe aliphatic polycarbonate polyol compositions as defined above and inthe embodiments and examples herein.

In certain embodiments the microcellular foam compositions comprise thereaction product of an A-side composition comprising polyfunctionalisocyanates with a B-side mixture of type PEC-B1, described above.

In certain embodiments the microcellular foam compositions comprise thereaction product of an A-side composition comprising polyfunctionalisocyanates with a B-side mixture of type PPC-B1, described above.

In certain embodiments, B-side formulations for microcellular foams haveviscosities below 100,000 centipoise, preferably below 6,000 centipoiseat 20 degrees celcius. Preferred B-side polyols have OH numbers between28 and 112. Preferred B-side polyols have acid numbers below 1.Preferred B-side polyols have functionalities between 1.9 and 3.0.Preferred A-side formulations have isocyanate functionalities below 2.7,most preferred between 2.0 and 2.5. Preferred finished microcellularfoams have closed cells and are between 0.2-0.7 grams per cubiccentimeter.

C. Rigid Foam Compositions

In one aspect, the present invention encompasses rigid foamcompositions. In certain embodiments, such rigid foam compositions arederived from a B-side mixture containing one or more of the aliphaticpolycarbonate polyol compositions as defined above and in theembodiments and examples herein.

In certain embodiments the rigid foam compositions comprise the reactionproduct of an A-side composition comprising polyfunctional isocyanateswith a B-side mixture of type PEC-B1, described above.

In certain embodiments the rigid foam compositions comprise the reactionproduct of an A-side composition comprising polyfunctional isocyanateswith a B-side mixture of type PPC-B1, described above.

In certain embodiments, B-side formulations for rigid foams haveviscosities below 100,000 centipoise, preferably below 40,000centipoise, and most preferably below 12,000 centipoise. PreferredB-side formulations have OH numbers between approximately 250 and 500.Typical B-side polyols have functionalities between 2 and 8. PreferredA-side formulations have isocyanate functionalities between 2.3 and 3.5.

In some embodiments, finished rigid foams have high insulating values,typically expressed as a “k value.” Preferably, these k values are <0.25watts/(mK), more preferred k vales of <0.20 watts/(mK), most preferred<0.15 watts/(mK). Some preferred rigid foams have combustionmodification requirements, such as achieving a Class 1 Flammabilityperformance on the UL 723 test.

D. Elastomer Compositions

In another aspect, the present invention encompasses polyurethaneelastomers derived from one or more of aliphatic polycarbonate polyolcompositions described above and in the specific embodiments andexamples disclosed herein. In certain embodiments, the polyurethaneelastomer compositions comprise the reaction product of one or morepolyisocyanates and a B-side mixture containing one or more of thealiphatic polycarbonate polyol compositions defined above.

In certain embodiments, B-side formulations for elastomers haveviscosities below 100,000 centipoise, preferably below 6,000 centipoiseat 20 degrees celcius. Preferred B-side polyols have OH numbers between28 and 112. Preferred B-side polyols have acid numbers below 1.Preferred B-side polyols have functionalities between 1.9 and 3.0.Preferred A-side formulations have isocyanate functionalities below 2.7.

E. Thermoplastic Compositions

In another aspect, the present invention encompasses thermoplasticcompositions derived from one or more of aliphatic polycarbonate polyolcompositions described above.

In certain embodiments, B-side formulations for thermoplastic elastomershave viscosities below 1,000,000 centipoise, preferably below 6,000centipoise at 20 degrees celcius. Preferred B-side polyols have OHnumbers between 28 and 112. Preferred B-side polyols have acid numbersbelow 1. Preferred B-side polyols have functionalities between 1.9 and2.1. Preferred A-side formulations have isocyanate functionalitiesbetween 1.9 and 2.1.

EXAMPLES

The present invention is illustrated by the following examples. It is tobe understood that the particular examples, materials, amounts, andprocedures are to be interpreted broadly in accordance with the scopeand spirit of the invention as set forth herein.

Presented below are the formulations of a variety of polyurethane foamsand elastomers. These materials were made using aliphatic polycarbonatepolyols as defined hereinabove. Specifically, the aliphaticpolycarbonate polyols used and identified in the examples below have thefollowing properties:

NOV-61-151 is a poly(propylene carbonate) polyol initiated withdipropylene glycol and having an Mn of 807 g/mol, a PDI of 1.276,greater than 99% —OH end groups, greater than 99% carbonate linkages(exclusive of the ether bond in the dipropylene glycol). This polyolconforms to formula P2B:

where each —Y is —H, and n is on average in the compositionapproximately 3.3.

NOV-53-047 is a poly(ethylene carbonate) polyol initiated with Fomrez®11-112, a commercially available polyester polyol (˜1,000 g/molpoly(diethylene glycol adipate)). The PEC polyol has an Mn of 1748g/mol, a PDI of 1.76, contains greater than 99% —OH end groups andcontains approximately 85% carbonate linkages (excluding the starter).This material conforms to formula Q8a:

where q is, on average in the composition, approximately 4.4, and n is,on average in the composition, approximately 4.3.

NOV-53-053 is a poly(ethylene carbonate) polyol initiated with Fomrez®11-112 and having an Mn of 2486 g/mol, a PDI of 1.41, containing greaterthan 99% —OH end groups and having approximately 85% carbonate linkages(excluding the starter). This material conforms to formula Q8a, where qis, on average in the composition, approximately 4.4, and n is onaverage in the composition approximately 8.4.

NOV-53-050 is a poly(ethylene carbonate) polyol initiated with Voranol®220-110N a polyether polyol (polypropylene oxide capped withpolyethylene oxide 1,000 g/mol). The polyol has an Mn of 2656 g/mol, aPDI of 1.10, contains greater than 99% —OH end groups and approximately85% carbonate linkages (excluding the starter). This material conformsto formula Q7b:

where q and q′ are, on average in the composition, approximately 8, andn is on average in the composition approximately 5.3.

NOV-53-052 is a poly(ethylene carbonate) polyol initiated with Voranol®220-110N and having an Mn of 1938 g/mol, a PDI of 1.11, containinggreater than 99% —OH end groups and approximately 85% carbonate linkages(excluding the starter). This material conforms to formula Q7b, where qand q′ are, on average in the composition, approximately 8, and n is onaverage in the composition approximately 9.4.

Example 1, Flexible Foam Formulations

In Example 1, a series of flexible polyurethane foams were formulatedand a qualitative assessment of their performance was completed. In allcases, the procedure for making these foams is as follows. First, allB-side components were dispensed in precise quantities into a cup,including all polyols, catalysts and other additives, and water as ablowing agent. They were then hand-mixed using a wooden stirring tool atroom temperature for a minimum of 30 seconds, until the mixture wasfully uniform. After the B-side was uniform, the A-side was added andthe mixture was again mixed by hand for a minimum of 15 seconds. Afterthe full formulation was well mixed, the mixture was transferred to anew cup and allowed to rise. The foams were then allowed to cure at roomtemperature. In the tables below, “Time to Cream” refers to the timeelapsed after the A-side was added to complete the mixture until themixture began to bubble, as indicated by the mixture becoming opaque.“Time to Gel” is the amount of time after the A-side was added until thepolyurethane foam network began to form, as indicated by pressing on thefoam with the mixing tool. “Time to Rise” is the amount of time afterthe A-side was added until the foam completed its full rise.

Flexible Foam Example 1B Description Grams Component Mondur MRSPolymeric MD rich in 2,4′-MDI isomer, 38.95 2.6 functional Nov-53-052PEC Polyol, 1940 Mw, 1.1 PDI, 2.0 56.95 Functional water Water as ablowing agent 2.28 T12 Gelling catalyst, dibutyl tin dilaurate 0.09Dabco 33LV Blowing catalyst 33% Triethylene 0.16 diamine in 67%dipropylene glycol DC5160 Silicone surfactant, general 0.57 polyurethanefoam use Results 45 Time to cream 2:30 Time to gel 2:50 Time to riseFoam reacts and rises OK, some shrinkage 1 hour, much shrinkageovernight

Flexible Foam Example 1A Description Grams Component Mondur MRSPolymeric MDI rich in 2,4′-MD isomer, 40.85 2.6 functional Nov-53-052PEC Polyol, 1940 Mw, 1.1 PDI, 2.0 56.95 Functional water Water as ablowing agent 2.28 T12 Gelling catalyst, dibutyl tin dilaurate 0.09Dabco 33LV Blowing catalyst 33% Triethylene 0.16 diamine in 67%dipropylene glycol DC5160 Silicone surfactant, general 0.57 polyurethanefoam use Results 55 Time to cream 2:40 Time to gel 3:20 Time to riseFoam reacts and rises OK, some shrinkage 1 hour, much shrinkageovernight

Flexible Foam Example 1C Description Grams Component Mondur MRSPolymeric MDI rich in 2,4′-MDI isomer, 38.40 2.6 functional Nov-53-050PEC Polyol, 2660 Mw, 1.1 PDI, 2.0 56.95 Functional water Water as ablowing agent 2.28 T12 Gelling catalyst, dibutyl tin dilaurate 0.09Dabco 33LV Blowing catalyst, 33% Triethylene 0.16 diamine in 67%dipropylene glycol DC 5160 Silicone surfactant, general 0.57polyurethane foam use Results 35 Time to cream 2:09 Time to gel 2:35Time to rise Foam reacts and rises OK, some shrinkage 1 hour, muchshrinkage overnight

Flexible Foam Example 1D Description Grams Component Mondur MRSPolymeric MDI rich in 2,4′-MDI isomer, 38.25 2.6 functional PEC 3500 MwPEC, 1.1 PDI, 2.0 functional 28.48 Nov-53-053 PEC Polyol, 2500 Mw, 1.1PDI, 2.0 28.48 Functional water Water as a blowing agent 2.28 T12Gelling catalyst, dibutyl tin dilaurate 0.09 Dabco 33LV Blowingcatalyst, 33% Triethylene 0.16 diamine in 67% dipropylene glycol DC 5160Silicone surfactant, general 0.57 polyurethane foam use Results 40 Timeto cream 2:02 Time to gel 0:00 Time to rise Foams nicely, no shrinkage,probably foam is too stiff to shrink

Example 2, Microcellular Foam Formulations

In Example 2, a series of microcellular polyurethane foams wereformulated and a qualitative assessment of their performance wascompleted. The procedure for making these foams is as follows. First,all B-side components were dispensed in precise quantities into a cup,including all polyols, catalysts and other additives, and water as ablowing agent. Most of the samples were then hand-mixed using a woodenstirring tool at room temperature for a minimum of 30 seconds, until themixture was fully uniform. For the larger samples 2L, 2M, and 2N, amechanical mixer at 1,100 RPM was used to complete the mixing of theB-side. After the B-side was uniform, the A-side was added and themixture was again mixed for a minimum of 15 seconds, by hand in mostcases and using the 1,100 RPM mechanical mixer for samples 2L, 2M, and2N. After the full formulation was well-mixed, the mixture was pouredinto a cup or, in the cases of 2L, 2M, and 2N, into an aluminum mold.The foams were then allowed to cure at room temperature. In the tablesbelow, “Time to Cream” refers to the time elapsed after the A-side wasadded to complete the mixture until the mixture began to bubble, asindicated by the mixture becoming opaque. “Time to Gel” is the amount oftime after the A-side was added until the polyurethane foam networkbegan to form, as indicated by pressing on the foam with the mixingtool. “Time to Rise” is the amount of time after the A-side was addeduntil the foam completed its full rise.

Microcellular Foam Example 2A Description Grams Component Suprasec 9612MDI prepolymer w/ polyester polyol, 29.64 2.01 functional Nov-53-047 PECPolyol, 1750 Mw, 1.76 PDI, 2.0 40.00 Functional water Water as a blowingagent 0.12 EG Ethylene Glycol 2.00 BD Butanediol 0.00 T12 Gellingcatalyst, dibutyl tin dilaurate 0.04 Dabco 1027 Blowing catalyst,tertiary amine in 30% 0.04 ethylene glycol Dabco 1028 Blowing catalyst,tertiary amine 0.00 catalyst in butane diol DC193 Silicone surfactant,used primarily in 0.40 shoe soles DC3043 Silicone surfactant, used for0.00 microcellular foam Results 39 Time to cream  0 Time to gel 3:00Time to rise Foam rises ok, shrinks back in less than 1 hour, 50%shrinkage overnight.

Microcellular Foam Example 2B Description Grams Component Suprasec 9612MDI prepolymer w/ polyester polyol, 29.64 2.01 functional Nov-53-047 PECPolyol, 1750 Mw, 1.76 PDI, 2.0 40.00 Functional water Water as a blowingagent 0.12 EG Ethylene Glycol 2.00 BD Butanediol 0.00 T12 Gellingcatalyst, dibutyl tin dilaurate 0.04 Dabco 1027 Blowing catalys,tertiary amine in 30% 0.03 ethylene glycol Dabco 1028 Blowing catalyst,tertiary amine 0.00 catalyst in butane diol DC193 Silicone surfactant,used primarily in 0.40 shoe soles DC3043 Silicone surfactant, used for0.00 microcellular foam Results 29 Time to cream  0 Time to gel 2:00Time to rise Foam rises ok, shrinks back in less than 1 hour, 50%shrinkage overnight, with cracks in foam.

Microcellular Foam Example 2D Description Grams Component Suprasec 9612MDI prepolymer w/ polyester polyol, 26.50 2.01 functional Nov-53-053 PECPolyol, 2500 Mw, 1.4 PDI, 2.0 40.00 Functional water Water as a blowingagent 0.12 EG Ethylene Glycol 2.00 BD Butanediol 0.00 T12 Gellingcatalyst, dibutyl tin dilaurate 0.03 Dabco 1027 Blowing catalyst,tertiary amine in 30% 0.04 ethylene glycol Dabco 1028 Blowing catalyst,tertiary amine 0.00 catalyst in butane diol DC193 Silicone surfactant,used primarily in 0.00 shoe soles DC3043 Silicone surfactant, used for0.40 microcellular foam Results 39 Time to cream 1.23 Time to gel 2:10Time to rise Foam rises OK, shrinks 50% overnight

Microcellular Foam Example 2C Description Grams Component Suprasec 9612MDI prepolymer w/ polyester polyol, 26.50 2.01 functional Nov-53-053 PECPolyol, 2500 Mw, 1.4 PDI, 2.0 40.00 Functional water Water as a blowingagent 0.12 EG Ethylene Glycol 2.00 BD Butanediol 0.00 T12 Gellingcatalyst, dibutyl tin dilaurate 0.04 Dabco 1027 Blowing catalyst,tertiary amine in 30% 0.04 ethylene glycol Dabco 1028 Blowing catalyst,tertiary amine 0.00 catalyst in butane diol DC193 Silicone surfactant,used primarily in 0.00 shoe soles DC3043 Silicone surfactant, used for0.40 microcellular foam Results 39 Time to cream 1.28 Time to gel 2:20Time to rise Foam rises Ok, shows shrink within an hour shrinks back 50%overnight

Microcellular Foam Example 2F Description Grams Component Suprasec 9612MDI prepolymer w/ polyester polyol, 25.69 2.01 functional Nov-53-053 PECPolyol, 2500 Mw, 1.4 PDI, 2.0 40.00 Functional water Water as a blowingagent 0.12 EG Ethylene Glycol 2.00 BD Butanediol 0.00 T12 Gellingcatalyst, dibutyl tin dilaurate 0.04 Dabco 1027 Blowing catalyst,tertiary amine in 30% 0.04 ethylene glycol Dabco 1028 Blowing catalyst,tertiary amine 0.00 catalyst in butane diol DC193 Silicone surfactant,used primarily in 0.00 shoe soles DC3043 Silicone surfactant, used for0.40 microcellular foam Results 38 Time to cream  0 Time to gel 1:35Time to rise Foam looks good, shrinks 20% overnight

Microcellular Foam Example 2E Description Grams Component Suprasec 9612MDI prepolymer w/ polyester polyol, 16.00 2.01 functional Mondur MRSPolymeric MDI rich in 2,4′-MDI isomer, 6.50 2.6 functional Nov-53-053PEC Polyol, 2500 Mw, 1.4 PDI, 2.0 40.00 Functional water Water as ablowing agent 0.12 EG Ethylene Glycol 2.00 BD Butanediol 0.00 T12Gelling catalyst, dibutyl tin dilaurate 0.04 Dabco 1027 Blowingcatalyst, tertiary amine in 30% 0.04 ethylene glycol Dabco 1028 Blowingcatalyst, tertiary amine 0.00 catalyst in butane diol DC193 Siliconesurfactant, used primarily in 0.00 shoe soles DC3043 Siliconesurfactant, used for 0.40 microcellular foam Results 36 Time to cream1.22 Time to gel 2:00 Time to rise Foam looks good, shrinks 30%overnight

Microcellular Foam Example 2H Description Grams Component Suprasec 9612MDI prepolymer w/ polyester polyol, 17.86 2.01 functional MM103 ModifiedMDI, 2.15 functional 7.15 Nov-53-053 PEC Polyol, 1940 Mw, 1.1 PDI, 2.040.00 Functional water Water as a blowing agent 0.12 EG Ethylene Glycol2.00 BD Butanediol 0.00 T12 Gelling catalyst, dibutyl tin dilaurate 0.04Dabco 1027 Blowing catalyst, tertiary amine in 30% 0.04 ethylene glycolDabco 1028 Blowing catalyst, tertiary amine 0.00 catalyst in butane diolDC193 Silicone surfactant, used primarily in 0.40 shoe soles DC3043Silicone surfactant, used for 0.00 microcellular foam Results 40 Time tocream 1:08 Time to gel 1:35 Time to rise Foam looks good, but shrinks20-40% overnight

Microcellular Foam Example 2G Description Grams Component Suprasec 9612MDI prepolymer w/ polyester polyol, 28.86 2.01 functional Nov-53-053 PECPolyol, 1940 Mw, 1.1 PDI, 2.0 40.00 Functional water Water as a blowingagent 0.12 EG Ethylene Glycol 2.00 BD Butanediol 0.00 T12 Gellingcatalyst, dibutyl tin dilaurate 0.04 Dabco 1027 Blowing catalyst,tertiary amine in 30% 0.04 ethylene glycol Dabco 1028 Blowing catalyst,tertiary amine 0.00 catalyst in butane diol DC193 Silicone surfactant,used primarily in 0.00 shoe soles DC3043 Silicone surfactant, used for0.40 microcellular foam Results 36 Time to cream 1:08 Time to gel 1:40Time to rise Foam looks ok, shrinks 20-40% overnight, soft and crumbly

Microcellular Foam Example 2I Description Grams Component Suprasec 9612MDI prepolymer w/ polyester polyol, 0.00 2.01 functional MM103 ModifiedMDI, 2.15 functional 17.04 Nov-53-053 PEC Polyol, 2500 Mw, 1.4 PDI, 2.040.00 Functional water Water as a blowing agent 0.12 EG Ethylene Glycol2.00 BD Butanediol 0.00 T12 Gelling catalyst, dibutyl tin dilaurate 0.04Dabco 1027 Blowing catalyst, tertiary amine in 30% 0.04 ethylene glycolDabco 1028 Blowing catalyst, tertiary amine 0.00 catalyst in butane diolDC193 Silicone surfactant, used primarily in 0.40 shoe soles DC3043Silicone surfactant, used for 0.00 microcellular foam Results 36 Time tocream 52 Time to gel 1:15 Time to rise Reacts fast, tough to pour aftermixing. 10% shrinkage overnight

Microcellular Foam Example 2J Description Grams Component Suprasec 9612MDI prepolymer w/ polyester polyol, 0.00 2.01 functional MM103 ModifiedMDI, 2.15 functional 19.05 Nov-53-053 PEC polyol, 2500 Mw, 1.4 PDI, 2.040.00 Functional water Water as a blowing agent 0.24 EG Ethylene Glycol2.00 BD Butanediol 0.00 T12 Gelling catalyst, dibutyl tin dilaurate 0.04Dabco 1027 Blowing catalyst, tertiary amine in 30% 0.04 ethylene glycolDabco 1028 Blowing catalyst, tertiary amine 0.00 catalyst in butane diolDC193 Silicone surfactant, used primarily in 0.40 shoe soles DC3043Silicone surfactant, used for 0.00 microcellular foam Results 36 Time tocream 53 Time to gel 1:20 Time to rise Foam looks OK, still tacky after10 min. 10% shrinkage overnight

Microcellular Foam Example 2L Description Grams Component Suprasec 9612MDI prepolymer w/ polyester polyol, 87.53 2.01 functional MM103 ModifiedMDI, 2.15 functional 10.50 Nov-53-050 PEC polyol, 2660 Mw, 1.1 PDI, 2.0150.00 Functional water Water as a blowing agent 0.75 EG Ethylene Glycol7.50 BD Butanediol 0.00 T12 Gelling catalyst, dibutyl tin dilaurate 0.08Dabco 1027 Blowing catalyst, tertiary amine in 30% 0.15 ethylene glycolDabco 1028 Blowing catalyst, tertiary amine 0.00 catalyst in butane diolDC193 Silicone surfactant, used primarily in 1.65 shoe soles DC3043Silicone surfactant, used for 0.00 microcellular foam Results 0 Time tocream 0 Time to gel 0:00 Time to rise Pouring plaque mold. Plaque looksgood, small shrinkage <10% noted on demold

Microcellular Foam Example 2K Description Grams Component Suprasec 9612MDI prepolymer w/ polyester polyol, 24.33 2.01 functional MM103 ModifiedMDI, 2.15 functional 2.80 Nov-53-050 PEC polyol, 2660 Mw, 1.1 PDI, 2.040.00 Functional water Water as a blowing agent 0.24 EG Ethylene Glycol2.00 BD Butanediol 0.00 T12 Gelling catalyst, dibutyl tin dilaurate 0.04Dabco 1027 Blowing catalyst, tertiary amine in 30% 0.04 ethylene glycolDabco 1028 Blowing catalyst, tertiary amine 0.00 catalyst in butane diolDC193 Silicone surfactant, used primarily in 0.40 shoe soles DC3043Silicone surfactant, used for 0.00 microcellular foam Results 43 Time tocream 1:07 Time to gel 2:10 Time to rise Foam looks good, <10% shrinkageovernight

Microcellular Foam Example 2N Description Grams Component Suprasec 9612MDI prepolymer w/ polyester polyol, 0.00 2.01 functional MM103 ModifiedMDI, 2.15 functional 69.02 Nov-53-053 PEC polyol, 2500 Mw, 1.4 PDI, 2.0150.00 Functional water Water as a blowing agent 0.75 EG Ethylene Glycol7.50 BD Butanediol 0.00 T12 Gelling catalyst, dibutyl tin dilaurate 0.05Dabco 1027 Blowing catalyst, tertiary amine in 30% 0.10 ethylene glycolDabco 1028 Blowing catalyst, tertiary amine 0.00 catalyst in butane diolDC193 Silicone surfactant, used primarily in 1.65 shoe soles DC3043Silicone surfactant, used for 0.00 microcellular foam Results 0 Time tocream 0 Time to gel 0:00 Time to rise Pouring plaque mold, Reaction wasfast, material did not rise to the full mold thickness.

Microcellular Foam Example 2M Description Grams Component Suprasec 9612MDI prepolymer w/ polyester polyol, 99.38 2.01 functional MM103 ModifiedMDI, 2.15 functional 10.50 Nov-53-052 PEC polyol, 1940 Mw, 1.1 PDI, 2.0150.00 Functional water Water as a blowing agent 0.75 EG Ethylene Glycol7.50 BD Butanediol 0.00 T12 Gelling catalyst, dibutyl tin dilaurate 0.08Dabco 1027 Blowing catalyst, tertiary amine in 30% 0.15 ethylene glycolDabco 1028 Blowing catalyst, tertiary amine 0.00 catalyst in butane diolDC193 Silicone surfactant, used primarily in 1.65 shoe soles DC3043Silicone surfactant, used for 0.00 microcellular foam Results 0 Time tocream 0 Time to gel 0:00 Time to rise Pouring plaque mold. Plaque looksgood, small shrinkage <10% noted on demold

Example 3, Rigid Foam Formulations

In Example 3, a series of rigid polyurethane foams were formulated and aqualitative assessment of their performance was completed. In all cases,the procedure for making these foams is as follows. First, all B-sidecomponents were dispensed in precise quantities into a cup, includingall polyols, catalysts and other additives, and water as a blowingagent. They were then hand-mixed using a wooden stirring tool at roomtemperature for a minimum of 30 seconds, until the mixture was fullyuniform. After the B-side was uniform, the A-side was added and themixture was again mixed by hand for a minimum of 15 seconds. After thefull formulation was well-mixed, the mixture was transferred to a newcup and allowed to rise. The foams were then allowed to cure at roomtemperature. In the tables below, “Time to Cream” refers to the timeelapsed after the A-side was added to complete the mixture until themixture began to bubble, as indicated by the mixture becoming opaque.“Time to Gel” is the amount of time after the A-side was added until thepolyurethane foam network began to form, as indicated by pressing on thefoam with the mixing tool. “Time to Rise” is the amount of time afterthe A-side was added until the foam completed its full rise.

Rigid Foam Example 3A Description Grams Component Mondur 489 PolymericMDI, 3.0 Functional 25.10 Nov-53-052 PEC Polyol, 1940 Mw, 1.1 PDI, 2.030.00 Functional water Water as a blowing agent 1.14 Dabco BL11 Blowingcatalyst 70% bis(2- 0.39 dimethylamino-ethyl) ether in 30% dipropyleneglycol Dabco 33LV Blowing catalyst, 33% Methylene 0.15 gamine in 67%dipropylene glycol DC5160 Silicone suriactant, general 0.36 polyurethanefoam use Results 1:00 Time to cream 2:27 Time to gel Foams will, shrinksovernight

Rigid Foam Example 3B Description Grams Component Mondur 489 PolymericMDI, 3.0 Functional 23.55 Nov-53-050 PEC Polyol, 2660 Mw, 1.1 PDI, 2.030.00 Functional water Water as a blowing agent 1.14 Dabco BL11 Blowingcatalyst, 70% bis(2- 0.39 dimethylamino-ethyl) ether in 30% dipropyleneglycol Dabco 33LV Blowing catalyst, 33% Triethylene 0.15 diamine in 67%dipropylene glycol DC5160 Silicone surfactant, general 0.36 polyurethanefoam use Results  1:00 Time to cream <2:00 Time to gel Foams OK, shrinksovernight

Rigid Foam Example 3D Description Grams Component Mondur 489 PolymericMDI, 3.0 Functional 30.76 Nov-61-151 PEC Polyol, 800 Mw, 1.3 PDI, 2.030.00 Functional water Water as a blowing agent 1.20 Dabco 1028 Blowingcatalyst, tertiary amine 0.45 catalyst in butane diol Dabco 33LV Blowingcatalyst, 33% Triethylene 0.15 diamine in 67% dipropylene glycol DC5160Silicone surfactant, general 0.36 polyurethane foam use Results 0:00Time to cream 0:00 Time to gel Foam starts to rise, then boils andcollapses

Rigid Foam Example 3C Description Grams Component Mondur 489 PolymericMDI, 3.0 Functional 23.90 Nov-53-053 PEC Polyol, 2500 Mw, 1.4 PDI, 2.030.00 Functional water Water as a blowing agent 1.14 Dabco BL11 Blowingcatalyst, 70% bis(2- 0.39 dimethylamino-ethyl) ether in 30% dipropyleneglycol Dabco 33LV Blowing catalyst, 33% Triethyene 0.15 diamine in 67%dipropylene glycol DC5160 Silicone surfactant, general 0.36 polyurethanefoam use Results 1:15 Time to cream 0:00 Time to gel Foam boils,collapses, like network did not develop strength until long afterblowing done

Rigid Foam Example 3E Description Grams Component Mondur 489 PolymericMDI, 3.0 Functional 30.76 Nov-61-151 PEC Polyol, 800 Mw, 1.3 PDI, 2.030.00 Functional water Water as a blowing agent 1.20 Dabco 1028 Blowingcatalyst, tertiary amine 0.45 catalyst in butane diol Dabco 33LV Blowingcatalyst, 33% Triethylene 0.15 diamine in 67% dipropylene glycol DC5160Silicone surfactant, general 0.36 polyurethane foam use Results 0:00Time to cream 0:00 Time to gel Foam rises with no shrink. Cells arecoarse, foam is friable

Rigid Foam Example 3F Description Grams Component Mondur 489 PolymericMDI, 3.0 Functional 30.76 Nov-53-050 PEC Polyol, 2660 Mw, 1.1 PDI, 2.05.00 Functional Nov-61-151 PEC Polyol, 800 Mw, 1.3 PDI, 2.0 30.00Functional water Water as a blowing agent 1.20 Dabco 1028 Blowingcatalyst, tertiary amine 0.45 catalyst in butane diol Db 33LV Blowingcatalyst, 33% Triethylene 0.15 diamine in 67% dipropylene glycol DC5160Silicone surfactant, general 0.36 polyurethane foam use Results  0:00Time to cream <1:40 Time to gel Foam rises with no shrink. Cells arecoarse, foam is friable

Example 4, Elastomer Formulations

In Example 4, a series of elastomers were formulated and a qualitativeassessment of their performance was completed. In all cases, theprocedure for making these elastomers is as follows. First, all B-sidecomponents were dispensed in precise quantities into a cup, includingall polyols, catalysts and other additives. They were then hand-mixedusing a wooden stirring tool at room temperature for a minimum of 30seconds, until the mixture was fully uniform. After the B-side wasuniform, the A-side was added and the mixture was again mixed by handfor a minimum of 15 seconds. After the full formulation was well-mixed,the mixture was poured into an aluminum mold and cured at 65 degreescelcius for one hour.

Elastomer Example 4B Description Grams Component Vibrathane 8000 MDIprepolymer w/ polyester polyol, 36.40 2.0 functional Nov-53-053 PECPolyol, 2500 Mw, 1.4 PDI, 2.0 50.00 Functional water Water as a blowingagent 0.00 EG Ethylene Glycol 0.00 BD Butanediol 4.00 T12 Gellingcatalyst, dibutyl tin dilaurate 0.05 Dabco 1027 Blowing catalyst,tertiary amine in 30% 0.00 ethylene glycol Dabco 1028 Blowing catalyst,tertiary amine 0.03 catalyst in butane diol DC193 Silicone surfactant,used primarily in 0.00 shoe soles DC3043 Silicone surfactant, used for0.00 microcellular foam Results Reacts fine. After overnight cure,elastomer is week, maybe 100% elongation

Elastomer Example 4A Description Grams Component Vibrathane 8000 MDIprepolymer w/ polyester polyol, 35.20 2.0 functional Nov-53-050 PECPolyol, 2660 Mw, 1.1 PDI, 2.0 50.00 Functional water Water as a blowingagent 0.00 EG Ethylene Glycol 0.00 BD Butanediol 4.00 T12 Gellingcatalyst, dibutyl tin dilaurate 0.05 Dabco 1027 Blowing catalyst,tertiary amine in 30% 0.00 ethylene glycol Dabco 1028 Blowing catalyst,tertiary amine 0.03 catalyst in butane diol DC193 Silicone surfactant,used primarily in 0.00 shoe soles DC3043 Silicone surfactant, used for0.00 microcellular foam Results Reacts fine. After overnight cure,elastomer is week, maybe 100% elongation

Elastomer Example 4D Description Grams Component Vibrathane 8000 MDIprepolymer w/ polyester polyol, 39.80 2.0 functional Nov-53-052 PECPolyol, 1940 Mw, 1.1 PDI, 2.0 50.00 Functional water Water as a blowingagent 0.00 EG Ethylene Glycol 0.00 BD Butanediol 4.00 T12 Gellingcatalyst, dibutyl tin dilaurate 0.11 Dabco 1027 Blowing catalyst,tertiary amine in 30% 0.00 ethylene glycol Dabco 1028 Blowing catalyst,tertiary amine 0.04 catalyst in butane diol DC193 Silicone surfactant,used primarily in 0.00 shoe soles DC3043 Silicone surfactant, used for0.00 microcellular foam Results reacts very slowly, cannot demold after1 hour, leave overnight; elastomer sample is brittle, little strength;After RT cure 2 months, the elastomer seems tougher, maybe 100%elongation

Elastomer Example 4C Description Grams Component Vibrathane 8000 MDIprepolymer w/ polyester polyol, 39.80 2.0 functional Nov-53-052 PECPolyol, 1940 Mw, 1.1 PDI, 2.0 50.00 Functional water Water as a blowingagent 0.00 EG Ethylene Glycol 0.00 BD Butanediol 4.00 T12 Gellingcatalyst, dibutyl tin dilaurate 0.05 Dabco 1027 Blowing catalyst,tertiary amine in 30% 0.00 ethylene glycol Dabco 1028 Blowing catalyst,tertiary amine 0.03 catalyst in butane diol DC193 Silicone surfactant,used primarily in 0.00 shoe soles DC3043 Silicone surfactant, used for0.00 microcellular foam Results reacts very slowly, cannot demold after1 hour, leave overnight; elastomer sample is brittle, little strength;After RT cure 2 months, the elastomer seems tougher, maybe 100%elongation

OTHER EMBODIMENTS

The foregoing has been a description of certain non-limiting embodimentsof the invention. Accordingly, it is to be understood that theembodiments of the invention herein described are merely illustrative ofthe application of the principles of the invention. Reference herein todetails of the illustrated embodiments is not intended to limit thescope of the claims, which themselves recite those features regarded asessential to the invention.

1-105. (canceled)
 106. A reaction mixture for preparing a rigidpolyurethane foam composition comprising: (a) a B-side mixturecomprising an aliphatic polycarbonate polyol derived fromcopolymerization of carbon dioxide and one or more epoxides, wherein thealiphatic polycarbonate polyol is characterized in that, on average inthe composition, the percentage of carbonate linkages is 85% or greater;one or more additional polyols selected from the group consisting ofpolyether polyols, polyester polyols, and mixtures of thereof; andoptionally one or more additives selected from a group consisting ofcolorants, UV stabilizers, flame retardants, antimicrobials,plasticizers, bacteriostats, cell-openers, antistatic agents,compatibilizers, blowing agents, surfactants, and catalysts for thereaction of a polyol with a polyisocyanate; and (b) an A side mixturecomprising one or more isocyanate compounds having two or moreisocyanate groups per molecule, and optionally comprising one or morediluents, solvents, surfactants, or coreactants.
 107. The reactionmixture according to claim 106, wherein the aliphatic polycarbonatepolyol comprises a primary repeating unit having a structure:

where R¹, R², R³, and R⁴ are, at each occurrence in the polymer chain,independently selected from the group consisting of —H, fluorine, anoptionally substituted C₁₋₄₀ aliphatic group, an optionally substitutedC₁₋₂₀ heteroaliphatic group, and an optionally substituted aryl group,where any two or more of R¹, R², R³, and R⁴ may optionally be takentogether with intervening atoms to form one or more optionallysubstituted rings optionally containing one or more heteroatoms. 108.The reaction mixture according to claim 106, wherein the aliphaticpolycarbonate polyol is poly(ethylene carbonate) derived fromcopolymerization of ethylene oxide and carbon dioxide.
 109. The reactionmixture according to claim 106, wherein the aliphatic polycarbonatepolyol is poly(propylene carbonate) derived from copolymerization ofpropylene oxide and carbon dioxide.
 110. The reaction mixture accordingto claim 106, wherein the aliphatic polycarbonate polyol has a numberaverage molecular weight (Ma) in the range of 500 g/mol to 3,000 g/mol.111. The reaction mixture according to claim 106, wherein the aliphaticpolycarbonate polyol is characterized in that it has a polydispersityindex less than 1.8.
 112. The reaction mixture according to claim 109,wherein the aliphatic polycarbonate polyol has a head-to-tail ratiogreater than 80%.
 113. The reaction mixture according to claim 106,wherein the one or more additional polyols comprise from 5 weightpercent to 95 weight percent of the total polyol content of the B-sidemixture.
 114. The reaction mixture according to claim 106, wherein thealiphatic polycarbonate polyol is characterized in that it has a Tggreater than −30° C.
 115. The reaction mixture according to claim 106,wherein the aliphatic polycarbonate polyol is characterized in that ithas a viscosity, as measured at a temperature of at least 20° C. butless than 70° C., of less than 30,000 cps.
 116. The reaction mixtureaccording to claim 106, wherein the aliphatic polycarbonate polyol ischaracterized in that at least 95% of the end groups are —OH groups.117. The reaction mixture according to claim 106, wherein the B-sidemixture comprises a catalyst for reaction of a polyol with apolyisocyanate, wherein the catalyst is a tertiary amine compound. 118.The reaction mixture according to claim 117, wherein the tertiary aminecompound is selected from a group consisting of triethylenediamine,N-methylmorpholine, N,N-dimethylcyclohexylamine,pentamethyldiethylenetriamine, tetramethylethylenediamine,1-methyl-4-dimethylaminoethylpiperazine,3-methoxy-N-dimethylpropylamine, N-ethylmorpholine, diethylethanolamine,N-cocomorpholine, N,N-dimethyl-N′,N′-dimethylisopropylpropylenediamine,N,N-diethyl-3-diethylaminopropylamine dimethylbenzylamine,1,8-Diazabicycloundec-7-ene (DBU), 1,4-diazabicyclo[2.2.2]octane(DABCO), triazabicyclodecene (TBD), and N-methyltriazabicyclodecene(MTBD).
 119. The reaction mixture according to claim 106, wherein theB-side mixture comprises polyols having OH numbers between 250 and 500.120. The reaction mixture according to claim 106, wherein the aliphaticpolycarbonate polyol has a structure P1:

wherein, R¹, R², R³, and R⁴ are, at each occurrence in the polymerchain, independently selected from the group consisting of —H, fluorine,an optionally substituted C₁₋₃₀ aliphatic group, and an optionallysubstituted C₁₋₂₀ heteroaliphatic group, and an optionally substitutedC₆₋₁₀ aryl group, where any two or more of R¹, R², R³, and R⁴ mayoptionally be taken together with intervening atoms to form one or moreoptionally substituted rings optionally containing one or moreheteroatoms; Y is, at each occurrence, independently —H or the site ofattachment to any of the chain-extending moieties described in theclasses and subclasses herein; n is at each occurrence, independently aninteger from about 3 to about 1,000;

is a multivalent moiety; and x and y are each independently an integerfrom 0 to 6, where the sum of x and y is between 2 and
 6. 121. Thereaction mixture according to claim 120, wherein

is derived from a dihydric alcohol.
 122. The reaction mixture accordingto claim 121, wherein the dihydric alcohol is selected from the groupconsisting of: 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol,1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol,2,2-dimethylpropane-1,3-diol, 2-butyl-2-ethylpropane-1,3-diol,2-methyl-2,4-pentane diol, 2-ethyl-1,3-hexane diol, 2-methyl-1,3-propanediol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol,1,12-dodecanediol, 2,2,4,4-tetramethylcyclobutane-1,3-diol,1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol,1,4-cyclohexanediol, 1,2-cyclohexanedimethanol,1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol,1,4-cyclohexanediethanol, isosorbide, glycerol monoesters, glycerolmonoethers, trimethylolpropane monoesters, trimethylolpropanemonoethers, pentaerythritol diesters, pentaerythritol diethers, andalkoxylated derivatives of any of these; wherein the dihydric alcohol isselected from the group consisting of: diethylene glycol, triethyleneglycol, tetraethylene glycol, higher poly(ethylene glycol), such asthose having number average molecular weights of from 220 to about 2000g/mol, dipropylene glycol, tripropylene glycol, and higherpoly(propylene glycols); or wherein the dihydric alcohol a polymericdiol selected from the group consisting of polyethers, polyesters,hydroxy-terminated polyolefins, polyethercopolyesters, polyetherpolycarbonates, polycarbonate-copolyesters, polyoxymethylene polymers,and alkoxylated analogs of any of these.
 123. The reaction mixtureaccording to claim 120, where

is derived from a polymeric diol or triol, the polymeric diol or triolis selected from the group consisting of polyethers, polyesters,hydroxy-terminated polyolefins, polyether-copolyesters, polyetherpolycarbonates, polyoxymethylene polymers, polycarbonate-copolyesters,and alkoxylated analogs of any of these.
 124. The reaction mixtureaccording to claim 120,

is derived from a tetraol or a polyhydric alcohol with more than fourhydroxyl groups.
 125. The reaction mixture according to claim 106,wherein the A side mixture comprises one or more isocyanate compoundshaving an isocyanate functionality between 2.3 and 3.5.
 126. Thereaction mixture according to claim 106, wherein the A-side mixturecomprises an isocyanate compound selected from a group consisting of1,6-hexamethylaminediisocyanate (HDI), isophorone diisocyanate (IPDI),4,4′methylene-bis(cyclohexyl isocyanate) (H₁₂MDI), 2,4-toluenediisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI),diphenylmethane-4,4′-diisocyanate (4,4′-MDI),diphenylmethane-2,4′-diisocyanate (2,4′-MDI), xylylene diisocyanate(XDI), 1,3-Bis(isocyanatomethyl)cyclohexane (H6-XDI),2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylenediisocyanate (TMDI), m-tetramethylxylylene diisocyanate (TMXDI),p-tetramethylxylylene diisocyanate (TMXDI), isocyanatomethyl-1,8-ictanediisocyanate (TIN), triphenylmethane-4,4′,4″triisocyanate,Tris(p-isocyanatomethyl)thiosulfate, 1,3-Bis(isocyanatomethyl)benzene,1,4-tetramethylene diisocyanate, trimethylhexane diisocyanate,1,6-hexamethylene diisocyanate, 1,4-cyclohexyl diisocyanate, lysinediisocyanate, and mixtures of any two or more of these.
 127. Thereaction mixture according to claim 106, wherein the one or moreadditional polyols comprises a polyester polyol.
 128. The reactionmixture according to claim 121, wherein: the B-side mixture comprisespolyols having OH numbers between 250 and 500; the aliphaticpolycarbonate polyol of the B-side mixture is characterized in that:each

and having an M_(n) between 1,000 g/mol and 3,000 g/mol; and the one ormore additional polyols comprises a polyester polyol.
 129. The reactionmixture of claim 128, wherein the B-side mixture further comprises oneor more of the following: a surfactant; a blowing agent; a catalyst forthe reaction of a polyol with a polyisocyanate, wherein the catalyst isa tertiary amine compound; and a flame retardant.
 130. The reactionmixture of claim 129, wherein the surfactant is a silicone-basedsurfactant; the blowing agent comprises water, a hydrocarbon, or acombination of each; the tertiary amine compound is selected from agroup consisting of triethylenediamine, N-methylmorpholine,N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine,tetramethylethylenediamine, 1-methyl-4-dimethylaminoethylpiperazine,3-methoxy-N-dimethylpropylamine, N-ethylmorpholine, diethylethanolamine,N-cocomorpholine, N,N-dimethyl-N′,N′-dimethylisopropylpropylenediamine,N,N-diethyl-3-diethylaminopropylamine dimethylbenzylamine,1,8-Diazabicycloundec-7-ene (DBU), 1,4-diazabicyclo[2.2.2]octane(DABCO), triazabicyclodecene (TBD), and N-methyltriazabicyclodecene(MTBD); and the flame retardant is a chlorinated phosphate ester,chlorinated paraffin, or a melamine powder.
 131. A process for preparinga rigid polyurethane foam composition comprising the steps of: providingthe reaction mixture according to claim 106; and allowing the rigidpolyurethane foam to rise.
 132. The reaction mixture according to claim106, wherein the one or more additional polyols comprise a polyolselected from the group consisting of materials available commerciallyunder the trade names: Voranol® (Dow), SpecFlex® (Dow), Tercarol® (Dow),Caradol® (Shell), Hyperliter®, Acclaim® (Bayer Material Science),Ultracel® (Bayer Material Science), Desmophen® (Bayer Material Science),and Arcol® (Bayer Material Science).